Novel compounds, processes and marking systems

ABSTRACT

Mono and bis substituted (arylsulfonyl)alkanes useful as color formers, particularly in carbonless duplicating and thermal marking systems, are prepared by the interaction of the appropriate aldehyde or dialdehyde with the appropriate aryl or heterocyclic moiety and the appropriate phenylsulfinic acid in the presence of a catalyst.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of our co-pending applicationSer. No. 931,654, filed Aug. 8, 1978, and now abandoned.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

This invention relates to novel compounds classified in the field oforganic chemistry as [(aryl)(indolyl)(arylsulfonyl)]methanes;[(heteryl)(indolyl)(arylsulfonyl)]methanes;[(alkyl)(indolyl)(arylsulfonyl)]methanes;[bis(indolyl)-bis(arylsulfonyl)]alkanes;[bis(aryl)(arylsulfonyl)]methanes;[(heteryl)(pyrrolyl)(arylsulfonyl)]methanes;[(aryl)(pyrrolyl)(arylsulfonyl)methanes; and[(aryl)(heteryl)(arylsulfonyl)]methanes useful as color precursors,particularly in the art of carbonless dupblicating as, for example, inpressure-sensitive systems and in thermal marking systems; to processesfor preparing said methanes and alkanes; and to pressure-sensitiveduplicating systems and thermal marking systems.

(b) Description of the Prior Art

Several classes of organic compounds of widely diverse structural typesare known to be useful as colorless precursors for carbonlessduplicating systems. Among the more important classes, there may benamed phenothiazines, for example, benzoyl leuco methylene blue;phthalides, for example, crystal violet lactone; fluorans, for example,2'-anilino-6'-diethylaminofluoran and2'-dibenzylamino-6'-diethylaminofluoran; arylsulfinate salts ofMichler's Hydrol; and various other types of colorless precursorscurrently employed in commercially accepted carbonless copy systems.Typical of the many such systems taught in the prior art are thosedescribed in U.S. Pat. Nos. 2,712,507, 2,800,457, 3,041,289 and4,000,087, which issued July 5, 1955, July 23, 1957, June 26, 1962 andDec. 28, 1976, respectively. Many of the color formers in the prior artsuffer one or more disadvantages such as low tinctorial strength, poorlight stability, low resistance to sublimation, low susceptibility tocopiability of the color-developed form in standard office copyingmachines, for example, a xerographic type of copier, and low solubilityin common organic solvents, the latter disadvantage thus requiring theuse of specialized and expensive solvents in order to obtainmicroencapsulated solutions of sufficient concentration for use inpressure-sensitive copying systems.

The following items to date appear to constitute the most relevant priorart with regard to the instant application.

Licari and Dougherty in the Journal of the American Chemical Society,76, 4039 (1954) describe the preparation and physical properties of3-indolemethyl phenyl sulfone and 3-indolemethyl p-toluenesulfone fromgramine and the corresponding sulfinic acid or its salts. It isindicated that the compounds might have bacteriostatic or plant growthfactor characteristics. Hellmann and Muller in Chemische Berichte, 98,638 (1965) describe the preparation and physical characteristics of3-benzolsulfonylmethylindol, 3-[p-toluolsulfonylmethyl]indol and3-[p-chlorobenzolsulfonylmethyl]indol from the interaction of indolecontaining an active hydrogen, paraformaldehyde and a sulfinic acidsodium salt in a mixture of acetic acid and N,N-dimethylformamide. Thereis no indication of the utility of the compounds. We have now discoveredthat the class of compounds of the types described by Licari andDougherty, and by Hellmann and Muller, are readily converted to coloredsubstances on thermal exposure. This property makes them useful forincorporation into thermal marking systems such as are used in recordingand in duplicating systems.

Treibs and Herrmann, in Hoppe-Seyler's Zeitschrift fuer PhysiologischeChemie 299, 168-185 (1955) [Chemical Abstracts 50: 944i (1956)] describethe preparation and physical characteristics of(2-methyl-3-indolyl)(p-dimethylaminophenyl)methene perchlorate from theinteraction of 2-methylindole and p-dimethylaminobenzaldehyde inperchloric acid. No indication of utility for the compounds is given inthe abstract.

U.S. Pat. No. 3,995,088, issued Nov. 30, 1976, discloses in mostpertinent part a series of normally colorless leuco methylene dyestuffsof the formula ##STR1## wherein Y represents an amino-substituted phenylresidue of the formula ##STR2## or an indolyl residue of the formula##STR3## wherein R₁ and R₂, independently of the other representhydrogen, alkyl with 1 to 12 carbon atoms, alkoxyalkyl with 2 to 8carbon atoms, benzyl or phenyl, R₃ is hydrogen, halogen, nitro, alkylhaving 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms, X₁represents hydrogen, alkyl with 1 to 12 carbon atoms, alkenyl with atmost 12 carbon atoms or benzyl, X₂ represents hydrogen, alkyl with 1 to12 carbon atoms or phenyl and the ring A is unsubstituted or substitutedby cyano, nitro, halogen, alkyl having 1 to 4 carbon atoms, alkoxyhaving 1 to 4 carbon atoms or acyl with 1 to 8 carbon atoms, and Zrepresents alkyl with 1 to 12 carbon atoms, alkenyl with at most 12carbon atoms, aryl, aralkyl, an heterocyclic radical or the residue ofan organic, particularly aliphatic or cycloaliphatic compound having aketomethylene group. The compounds are claimed as being useful as colorformers in pressure-sensitive copying paper.

U.S. Pat. No. 3,193,404, issued July 6, 1965, discloses in mostpertinent part, a series of normally colorless associated dye saltsderived from interaction of sulfinic acid and benzhydrols. The salts arestated to be useful as color formers in carbonless transfer sheets andare represented by the formula ##STR4## wherein R is dimethylamino,diethylamino or methoxy, R¹ is dimethylamino or diethylamino and Y is aC₁ to C₁₂ aliphatic group, phenyl or substituted phenyl.

German Offenlegungschrift No. 2,243,322, published Mar. 21, 1974,discloses in most pertinent part, a process for the preparation of aseries of compounds having the formula ##STR5## in which Z¹, Z², Z³ andZ⁴, independently of each other, signify hydrogen, if need be,substituted alkyl, cycloalkyl, aralkyl or aryl, and Z¹ and Z² and Z³ andZ⁴ together with the nitrogen represent a heterocycle or at timescombined with one of the radicals at the ortho-position of the benzenering produce a condensed heterocycle, and Z⁵ is hydrogen, a halogen, analkyl or alkoxy and Z⁶ represents a hydrogen, halogen, alkyl or alkoxyand Z designates, if need be, a substituted aralkylamino,cycloalkylamino, arylamino, a radical bound via a heterocyclic nitrogenor arylsulfonyl. The compounds are said to be formed by the oxidation ofa substituted diphenylmethane and subsequent reaction with a compound ofthe formula ZM wherein Z is as defined above and M is hydrogen, or asodium, potassium or ammonium cation. The compounds are disclosed asbeing useful as reaction dyestuffs for carbonless copying procedures.

German Offenlegungschrift No. 2,208,611, which was published Sept. 6,1973, discloses a process for the preparation of a series of compoundsof the formula ##STR6## wherein R is methyl or ethyl and R¹ is phenyl ornaphthyl substituted by an alkyl, chloro, nitro or alkoxy whichcomprises the condensation of the appropriate leucauramine of theformula ##STR7## and a sulfinic acid of the formula R¹ -SO₂ H in anacidic medium.

Hinsberg, in Chemische Berichte, 50 468-473 (1917), describes thepreparation and physical properties ofphenyl[4,4'-bis(dimethylamino)benzhydryl]sulfone prepared by thereaction of 4,4'-bis(dimethylamino)benzhydrol with benzene sulfonic acidin dilute hydrochloric acid. There is no indication of utility given forthe product.

SUMMARY OF THE INVENTION

The present invention provides novel[(aryl)(indolyl)(arylsulfonyl)]methanes;[(heteryl)(indolyl)(arylsulfonyl)]methanes selected from among[bis(indolyl)(arylsulfonyl)]methanes,[(pyrrolyl)(indolyl)(arylsulfonyl)]methanes,[(carbazolyl)(indolyl)(arylsulfonyl]methanes,[(furanyl)(indolyl)(arylsulfonyl)]methanes,[(thienyl)(indolyl)(arylsulfonyl)]methanes,[(pyridinyl)(indolyl)(arylsulfonyl)]methanes,[(julolidinyl)(indolyl)(arylsulfonyl)]methanes;[(aryl)(indolyl)(arylsulfonyl)]methanes;[bis(indolyl)-bis(arylsulfonyl)]alkanes;[bis(aryl)(arylsulfonyl)]methanes;[(aryl)(julolidinyl)(arylsulfonyl)]methanes;[(aryl)(pyrrolyl)(arylsulfonyl)]methanes;[(thienyl)(pyrrolyl)(arylsulfonyl]methanes;[(furanyl)(pyrrolyl)(arylsulfonyl)]methanes;[bis(pyrrolyl)(arylsulfonyl)]methanes;[(pyridinyl)(pyrrolyl)(arylsulfonyl)]methanes; and[(carbazolyl)(pyrrolyl)(arylsulfonyl)]methanes which are useful as colorprecursors in pressure-sensitive duplicating systems and in thermalmarking systems. The compounds develop colored images of good toexcellent tinctorial strength and xerographic copiability and enhancedsolubility in common organic solvents.

In one of its composition of matter aspects, the invention relates to aseries of [(aryl)(indolyl)(arylsulfonyl)]methanes,[(heteryl)(indolyl)(arylsulfonyl)]methanes,[(alkyl)(indolyl)(arylsulfonyl)]methanes and[bis(indolyl)-bis(arylsulfonyl)]alkanes which are useful as colorprecursors in pressure-sensitive carbonless duplicating systems andthermal marking systems.

In the second of its composition of matter aspects, the inventionrelates to [bis(aryl)(arylsulfonyl)]methanes and[(aryl)(heteryl)(arylsulfonyl)]methanes which are useful as colorprecursors in pressure-sensitive carbonless duplicating systems andthermal marking systems.

In the third of its composition of matter aspects, the invention relatesto [(heteryl)(pyrrolyl)(arylsulfonyl)]methanes and[(aryl)(pyrrolyl)(arylsulfonyl)]methanes which are useful as colorprecursors in pressure-sensitive carbonless duplicating systems andthermal marking systems.

In one of its process aspects, the invention relates to a process forpreparing a [(A)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methane which comprises interacting analdehyde of the formula A-CHO with a 1-R¹ -2-R² -5/6-R³ -indole, and aR-phenylsulfinic acid in the presence of a catalyst.

In a second of its process aspects, the invention relates to a processfor preparing a [αω-bis(indolyl)-α,ω-bis(arylsulfonyl)]alkane whichcomprises interacting a 1-R¹ -2-R² -5/6-R³ -indole and aR-phenylsulfinic acid with a dialdehyde, (CH₂)_(m) (CHO)₂, in thepresence of a catalyst.

In a third of its process aspects, the invention relates to a processfor preparing a [60 ,ω-bis(indolyl)-α,ω-bis(arylsulfonyl)]butane whichcomprises interacting a 1-R¹ -2-R² -5/6-R³ -indole and aR-phenylsulfinic acid with a 2,5-di(C₁ -C₃ alkoxy)tetrahydrofuran, inthe presence of a catalyst.

In a fourth of its process aspects, the invention relates to a processfor preparing a [(Q)(2-R⁵ -4-R⁶ -phenyl)(R-phenylsulfonyl)]methane whichcomprises interacting an appropriate 2-R⁵ -4-R⁶ -benzaldehyde with acompound of the formula Q-H and an appropriate R-phenylsulfinic acid inthe presence of a catalyst.

In a fifth of its process aspects, the invention relates to a processfor preparing a [(Z)(1-R⁸ -2-pyrrolyl)(R-phenylsulfonyl)]methane whichcomprises interacting an appropriate aldehyde of the formula ZCHO withthe appropriate 1-R⁸ pyrrole and an appropriate R-phenylsulfinic acid inthe presence of a catalyst.

The present invention provides as articles of manufacturepressure-sensitive carbonless duplicating systems and thermal markingsystems each containing a color-forming substance comprising an[(aryl)(indolyl)(arylsulfonyl)]methane, a[(heteryl)(indolyl)(arylsulfonyl)]methane, an[(alkyl)(indolyl)(arylsulfonyl]methane, a[bis(indolyl)-bis(arylsulfonyl)]alkane, a[bis(aryl)(arylsulfonyl)]methane or a[(aryl)(heteryl)(arylsulfonyl)]methane,[(heteryl)(pyrrolyl)(arylsulfonyl)]methane, or[(aryl)(pyrrolyl)(arylsulfonyl)]methane as well as mixtures thereof.

DETAILED DESCRIPTION INCLUSIVE OF THE PREFERRED EMBODIMENTS

More specifically, this invention, in its first composition of matteraspect, residues in the novel alkanes, which are particularly useful ascolorless precursors in the art of carbonless duplicating and thermalmarking, and which are [(A)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methanes of the formula ##STR8## wherein:A represents a moiety selected from the class having the formulas##STR9## in which R represents one or two of hydrogen, C₁ to C₁₂ alkyl,C₁ to C₃ alkoxy, halo, nitro or acetamido; R¹ and R^(1') representhydrogen, C₁ to C₁₈ alkyl, C₂ to C₄ alkenyl, benzyl or benzylsubstituted in the benzene ring by one or two of halo or C₁ to C₃ alkyl;R² and R^(2') represent hydrogen, C₁ to C₃ alkyl or phenyl; R³ andR^(3') represent one or two of hydrogen, C₁ to C₃ alkyl, C₁ to C₃alkoxy, halo or nitro; R⁴ represents hydrogen or methyl; R⁵ representshydrogen, dialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl, C₁to C₃ alkyl, C₁ to C₄ alkoxy or halo; R⁶ represents hydrogen, C₁ to C₃alkyl, C₁ to C₃ alkoxy, halo, dialkylamino in which alkyl isnon-tertiary C₁ to C₄ or N-alkylbenzylamino, in which alkyl isnon-tertiary C₁ to C₄ and benzyl may be substituted in the benzene ringby one or two of halo or C₁ to C₃ alkyl; R⁷ and R⁸ represent hydrogen,C₁ to C₃ alkyl or phenyl; n is an integer from zero to ten with theproviso that when n is zero and R⁴ is hydrogen or methyl, R¹, R² and R³cannot simultaneously be hydrogen; and m represents an integer from oneto six.

In a first particular embodiment in accordance with the firstcomposition of matter aspect, the invention sought to be patentedresides in the novel [(2-R⁵ -4-R⁶ -phenyl)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methanes of Formula I wherein A is 2-R⁵-4-R⁶ -phenyl according to the formula ##STR10## wherein R, R¹, R², R³,R⁵ and R⁶ each have the same respective meanings given in Formula I.

In the second particular embodiment in accordance with the firstcomposition of matter aspect, the invention sought to be patentedresides in the novel [(1-R¹ -2-R² -5/6-R³ -3-indolyl)(1-R^(1') -2-R^(2')-5/6-R^(3') -3-indolyl)(R-phenylsulfonyl)]methane of Formula I wherein Ais 1-R^(1') -2-R^(2') -5/6-R^(3') -3-indolyl according to the formula##STR11## wherein R, R¹, R^(1'), R², R^(2'), R³ and R^(3') each have thesame respective meanings given in Formula I.

In a third particular embodiment in accordance with the firstcomposition of matter aspect, the invention sought to be patentedresides in the novel [(9-R⁷ -3-carbazoyl)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methanes of Formula I wherein A is 9-R⁷-3-carbazolyl according to the formula ##STR12## wherein R, R¹, R², R³and R⁷ each have the same meanings given in Formula I.

In a fourth particular embodiment in accordance with the firstcomposition of matter aspect, the invention sought to be patentedresides in the novel [1-R⁸ -2-pyrrolyl)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methanes of Formula I wherein A is 1-R⁸-2-pyrrolyl according to the formula ##STR13## wherein R, R¹, R², R³ andR⁸ each have the same respective meanings given in Formula I.

In a fifth particular embodiment in accordance with the firstcomposition of matter aspect, the invention sought to be patentedresides in the novel [(2-furanyl)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methanes of Formula I wherein A is2-furanyl according to the formula ##STR14## wherein R, R¹, R² and R³each have the same respective meanings given in Formula I.

In a sixth particular embodiment in accordance with the firstcomposition of matter aspect, the invention sought to be patentedresides in the novel [(2-thienyl)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methanes of Formula I wherein A is2-thienyl according to the formula ##STR15## wherein R, R¹, R² and R³each have the same respective meanings given in Formula I.

In a seventh particular embodiment in accordance with the firstcomposition of matter aspect, the invention sought to be patentedresides in the novel [(2-pyridinyl)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methanes of Formula I wherein A is2-pyridinyl according to the formula ##STR16## wherein R, R¹, R² and R³each have the same respective meanings given in Formula I.

In an eighth particular embodiment in accordance with the firstcomposition of matter aspect, the invention sought to be patentedresides in the novel [(9-julolidinyl)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]meythanes of Formula I wherein A is9-julolidinyl according to the formula ##STR17## wherein R, R¹, R² andR³ each have the same respective meanings given in Formula I.

In a ninth particular embodiment in accordance with the firstcomposition of matter aspect, the invention sought to be patentedresides in the novel {[R⁴ --CH₂)_(n) ](1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)}methanes of Formula I wherein A is R⁴--CH₂)_(n) -- according to the formula ##STR18## wherein R, R¹, R², R³,R⁴ and n each have the same respective meanings given in Formula I.

In a tenth particular embodiment in accordance with the firstcomposition of matter aspect, the invention sought to be patentedresides in the novel [α,ω-bis(1-R¹ -2-R² -5/6-R³-3-indolyl)-α,ω-bis(R-phenylsulfonyl)]alkanes of Formula I wherein A is##STR19## according to the formula ##STR20## wherein R, R¹, R² and R³each have the same respective meanings given in Formula I.

This invention, in its second composition of matter aspect, resides inthe novel methanes, which are particularly useful as colorlessprecursors in the art of carbonless duplicating and thermal marking, andwhich are [(B)(2-R⁵ -4-R⁶ -phenyl)(R-phenylsulfonyl)]methanes having theformula ##STR21## wherein: B represents a moiety selected from the classhaving the formulas ##STR22## R represents one or two of hydrogen, C₁ toC₁₂ alkyl, C₁ to C₃ alkoxy, halo, nitro or acetamido; R⁵ and R^(5")represent hydrogen, dialkylamino in which alkyl is non-tertiary C₁ to C₄alkyl, C₁ to C₃ alkyl, C₁ to C₄ alkoxy or halo; R⁶ represents hydrogen,C₁ to C₃ alkyl, C₁ to C₃ alkoxy, halo, dialkylamino in which alkyl isnon-tertiary C₁ to C₄ or N-alkylbenzylamino in which alkyl isnon-tertiary C₁ to C₄ and benzyl may be substituted in the benzene ringby one or two of halo or C₁ to C₃ alkyl; R^(6") represents hydrogen, C₁to C₃ alkyl or halo with the provisos (i) that when R⁵ or R^(5") isdialkylamino, R^(6") represents dialkylamino in which alkyl isnon-tertiary C₁ to C₄ or N-alkylbenzyl amino in which alkyl isnon-tertiary C₁ to C₄ and benzyl may be substituted in the benzene ringby one or two of halo or C₁ to C₃ alkyl and (ii) when R⁵ or R^(5") isother than hydrogen, R^(6") is C₁ to C₃ alkoxy.

In a first particular embodiment in accordance with the secondcomposition of matter aspect, the invention sought to be patentedresides in the novel [(2-R^(5") -4-R^(6") -phenyl)(2-R⁵ -4-R⁶-phenyl)(R-phenylsulfonyl)]methanes of Formula XII wherein B, is2-R^(5") -4-R^(6") -phenyl according to the formula ##STR23## wherein R,R⁵, R^(5"), R⁶ and R^(6") each have the same respective meanings givenin Formula XII.

In a second particular embodiment in accordance with the secondcomposition of matter aspect, the invention sought to be patentedresides in the novel [(9-julolidinyl)(2-R⁵ -4-R⁶-phenyl)(R-phenylsulfonyl)]methane of Formula XII wherein B is9-julolidinyl according to the formula ##STR24## wherein R, R⁵ and R⁶each have the same respective meanings given in Formula XII.

This invention, in its third composition of matter aspects, resides inthe novel methanes, which are particularly useful as colorlessprecursors in the art of carbonless duplicating and thermal marking, andwhich are [(Z)(1-R⁸ -2-pyrrolyl)(R-phenylsulfonyl)]methanes having theformula ##STR25## wherein Z represents a moiety selected from the classhaving the formulas ##STR26## R represents one or two of hydrogen, C₁ toC₁₂ alkyl, C₁ to C₃ alkoxy, halo, nitro or acetamido; R⁵ representshydrogen, dialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl, C₁to C₃ alkyl, C₁ to C₄ alkoxy or halo; R⁶ represents hydrogen, C₁ to C₃alkyl, C₁ to C₃ alkoxy, halo, dialkylamino in which alkyl isnon-tertiary C₁ to C₄ or N-alkylbenzylamino in which alkyl isnon-tertiary C₁ to C₄ and benzyl may be substituted in the benzene ringby one or two of halo or C₁ to C₃ alkyl; and R⁷ and R⁸ representhydrogen, C₁ to C₃ alkyl or phenyl.

In a first particular embodiment in accordance with the thirdcomposition of matter aspect, the invention sought to be patentedresides in the novel [(2-R⁵ -4-R⁶ -phenyl)(1-R⁸-2-pyrrolyl)(R-phenylsulfonyl)]methanes of Formula XVI wherein Z is 2-R⁵-4-R⁶ -phenyl according to the formula ##STR27## wherein R, R⁵, R⁶ andR⁸ each have the same respective meanings given in Formula XVI.

In a second particular embodiment in accordance with the thirdcomposition of matter aspect, the invention sought to be patentedresides in the novel [(2-thienyl)(1-R⁸-2-pyrrolyl)(R-phenylsulfonyl)]methanes of Formula XVI wherein Z is2-thienyl according to the formula ##STR28## wherein R and R⁸ each havethe same meanings given in Formula XVI.

In a third particular embodiment in accordance with the thirdcomposition of matter aspect, the invention sought to be patentedresides in the novel [(2-furanyl)(1-R⁸-2-pyrrolyl)(R-phenylsulfonyl)]methanes of Formula XVI wherein Z is2-furanyl according to the formula ##STR29## wherein R and R⁸ each havethe same meanings given in Formula XVI.

In a fourth particular embodiment in accordance with the thirdcomposition of matter aspect, the invention sought to be patentedresides in the novel [(9-R⁷ -3-carbazolyl)(1-R⁸-2-pyrrolyl)(R-phenylsulfonyl)]methanes of Formula XVI wherein Z is 9-R⁷-3-carbazolyl according to the formula ##STR30## wherein R, R⁷ and R⁸each have the same meanings given in Formula XVI.

In one of its process aspects, the invention sought to be patentedresides in a process for preparing a [(A)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methane according to Formula I wherein Arepresents a moiety selected from the class having the formulas##STR31## which comprises interacting in approximately equal molecularproportions an appropriate 1-R¹ -2-R² -5/6-R³ -indole with anR-phenylsulfinic acid and an appropriate aldehyde of the formula A-CHOin the presence of a catalyst wherein A is as above defined and each ofR, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R^(1'), R^(2'), R^(3') and n have thesame respective meanings given in Formula I.

In a second of its process aspects, the invention sought to be patentedresides in the process for preparing a [α,ω-bis(1-R¹ -2-R² -5/6-R³-3-indolyl)-α,ω-bis(R-phenylsulfonyl)]alkane according to Formula XIwhich comprises interacting approximately two molecular proportions ofan appropriate 1-R¹ -2-R² -5/6-R³ -indole with approximately twomolecular equivalents of an appropriate R-phenylsulfinic acid andapproximately one molecular equivalent of an appropriate dialdehyde ofthe formula (CH₂)_(m) (CHO)₂ in the presence of a catalyst wherein R,R¹, R², R³ and m each have the same respective meanings given in FormulaXI.

In a third of its process aspects, the invention sought to be patentedresides in the process for preparing a [1,4-bis(1-R¹ -2-R² -5/6-R³-3-indolyl)-1,4-bis(R-phenylsulfonyl)]butane according to Formula XIwherein m is two which comprises interacting approximately two molecularproportions of an appropriate 1-R¹ -2-R² -5/6-R³ -indole withapproximately two molecular proportions of an appropriateR-phenylsulfinic acid and approximately one molecular proportion of anappropriate 2,5-di(C₁ -C₃ alkoxy)tetrahydrofuran in the presence of acatalyst wherein R, R¹, R² and R³ each have the same respective meaningsgiven in Formula XI.

In a fourth of its process aspects, the invention sought to be patentedresides in the process for preparing a [(Q)(2-R⁵ -4-R⁶-phenyl)-(R-phenylsulfonyl)]methane having the formula ##STR32##wherein: Q represents a moiety selected from the class having theformulas ##STR33## R represents one or two of hydrogen, C₁ to C₁₂ alkyl,C₁ to C₃ alkoxy, halo, nitro or acetamido; R⁵ and R^(5') representhydrogen, dialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl, C₁to C₃ alkyl, C₁ to C₄ alkoxy or halo; and R⁶ and R^(6') representhydrogen, C₁ to C₃ alkyl, C₁ to C₃ alkoxy, halo, dialkylamino in whichalkyl is non-tertiary C₁ to C₄ or N-alkylbenzylamino in which alkyl isnon-tertiary C₁ to to C₄ and benzyl may be substituted in the benzenering by one or two of halo or C₁ to C₃ alkyl; which comprisesinteracting in approximately equal molecular proportions an appropriate2-R⁵ -4-R⁶ -benzaldehyde with an appropriate compound of the formula Q-Hand an appropriate R-phenylsulfinic acid in the presence of a catalyst.

In a fifth of its process aspects, the invention sought to be patentedresides in the process for preparing a [(Z)(1-R⁸-2-pyrrolyl)(R-phenylsulfonyl)]methane according to Formula XVI whereinZ represents a moiety selected from the class having the formulas##STR34## which comprises interacting in approximately equal molecularproportions an appropriate 1-R⁸ -pyrrole with a R-phenylsulfinic acidand an appropriate aldehyde of the formula Z-CHO in the presence of acatalyst wherein Z is as above defined and each of R and R⁸ have thesame respective meanings given in Formula XVI.

In its article of manufacture aspect, the invention sought to bepatented resides in a pressure-sensitive carbonless duplicating systemor a thermal marking system containing as a color-forming substance a[(A)(1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)]methane accordingto Formula I, a [(B)(2-R⁵ -4-R⁶ -phenyl)(R-phenylsulfonyl)]methaneaccording to Formula XII, a [α,ω-bis(1-R¹ -2-R² -5/6-R³-indolyl)-α,ω-bis(R-phenylsulfonyl)]-alkane according to Formula XI or a[(Z)(1-R⁸ -2-pyrrolyl)(R-phenylsulfonyl)]methane according to FormulaXVI wherein R, R¹, R², R³, R⁵, R⁶, R⁸, A, B and Z each have the samerespective meanings given in relation to Formulas I, XI, XII or XVI.

A particular embodiment sought to be patented resides in apressure-sensitive transfer sheet, adapted for use with a receivingsheet having an electron accepting layer, comprising a support sheetcoated on one side with a layer of pressure-rupturable microcapsulescontaining a liquid solution of a color-forming substance comprising atleast one compound depicted by Formula I, by Formula XII or by FormulaXVI.

Another particular embodiment sought to be patented resides in a heatresponsive record material comprising a support sheet coated on one sidewith a layer containing a mixture comprising at least one color-formingcompound having Formula I, Formula XI, Formula XII or Formula XVI and anacidic developer arranged such that application of heat will produce amark-forming reaction between the color-forming compound and the acidicdeveloper.

Preferred articles within the ambit of the particular embodiments abovedescribed are those wherein the color-forming component comprises a[(2-R⁵ -4-R⁶ -phenyl)(1-R¹ -2-R² -5/6-R³-indolyl)(R-phenylsulfonyl)]methane according to Formula II wherein R,R¹, R², R³, R⁵ and R⁶ each have the same respective meanings given inrelation to Formula II, a [(1-R¹ -2-R² -5/6-R³ -3-indolyl)(1-R^(1')-2-R^(2') -5/6-R^(3') -3-indolyl)(R-phenylsulfonyl)]methane according toFormula III wherein R, R^(1'), R², R^(2'), R³ and R^(3') each have thesame respective meanings given in relation to Formula III, a[(2-furanyl)(1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)]methaneaccording to Formula VI wherein R, R¹, R² and R³ each have the samerespective meanings given in relation to Formula VI, a [(2-thienyl)(1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)]methaneaccording to Formula VII wherein R, R¹, R² and R³ each have the samerespective meanings given in relation to Formula VII, a [(1-R⁸-2-pyrrolyl)(1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)]methaneaccording to Formula V wherein R, R¹, R², R³ and R⁸ each have the samerespective meanings given in relation to Formula V, a [α,ω-bis(1-R¹-2-R² -5/6-R³ -3-indolyl)-α,ω-bis(R-phenylsulfonyl)]alkane according toFormula XI wherein R, R¹, R² and R³ each have the same respectivemeanings given in relation to Formula XI, a [(2-R^(5") -4-R^(6")-phenyl)(2-R⁵ -4-R⁶ -phenyl)(R-phenylsulfonyl)]methane according toFormula XIII wherein R, R⁵, R^(5'), R⁶ and R^(6') each have the samerespective meanings given in relation to Formula XIV, a [(2-R⁵ -4-R⁶phenyl)(1-R⁸ -2-pyrrolyl)(R-phenylsulfonyl)]methane according to FormulaXVII wherein R, R⁵, R⁶ and R⁸ each have the same respective meaningsgiven in relation to Formula XVII, a [(2-thienyl)(1-R⁸-2-pyrrolyl)(R-phenylsulfonyl)]methane according to Formula XVIIIwherein R and R⁸ each have the same respective meanings given inrelation to Formula XVIII or a [(9-R⁷ -3-carbazolyl)(1-R⁸-2-pyrrolyl)(R-phenylsulfonyl)]methane according to Formula XX whereinR, R⁷ and R⁸ each have the same respective meanings given in relation toFormula XX.

The compounds of Formula I in which A is R⁴ --(CH₂)_(n), the {[R⁴--CH₂)_(n) ](1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)}methanesdepicted by Formula X, have also been found to produce colored images inred to purple shades when paper treated with them without an aciddeveloper is contacted with a heated stylus or heated type. This groupof compounds of the invention are decidedly advantageous over thosecompounds employed in thermal duplicating systems which require theincorporation of an acidic developer such as bisphenol A in that theyafford thermal copy systems containing only a single component for theproduction of a colored image. Thus, in another of its aspects, thisinvention resides in a thermal paper marking system containing as acolor forming substance a {[R⁴ --CH₂)_(n) ](1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)}methane wherein R, R¹, R², R³, R⁴ and neach have the same respective meanings given in relation to Formula X.

As used herein the term "halo" includes chloro, fluoro, bromo and iodo.Chloro is the preferred halo substituent because of the relatively lowcost and ease of preparation of the required chloro-substitutedintermediates and because the other halogens offer no particularadvantages over chloro. However, the other above-named halo substituentsare also satisfactory.

The term dialkylamino in which alkyl is "non-tertiary C₁ to C₄ alkyl"denotes saturated, acyclic groups which may be straight or branched asexemplified by dimethylamino, diethylamino, ethylmethylamino,dipropylamino, dibutylamino, isobutylmethylamino and the like.

As used herein the terms "C₁ to C₃ alkyl", C₁ to C₁₂ alkyl" and "C₁ toC₁₈ alkyl" denote saturated monovalent straight or branched aliphatichydrocarbon radicals including methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, amyl, 1-methylbutyl, 3-methylbutyl, hexyl,isohexyl, heptyl, isoheptyl, octyl, isooctyl, 2-ethylhexyl, nonyl,3-ethylheptyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,1,3,5-trimethylhexyl, 1,5-dimethyl-4-ethylhexyl, 5-methyl-2-butyl-hexyl,2-propylnonyl, 2-butyloctyl, 2-pentylnonyl, 1,2-dimethylhexadecyl andthe like.

The terms "C₁ to C₃ " alkoxy and "C₁ to C₄ alkoxy" include saturated,acyclic, straight or branch-chained groups such as methoxy, ethoxy,propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy.

As used herein, the term "C₂ to C₄ alkenyl" means a monovalent aliphaticradical possessing a single double bond, for example, ethenyl (orvinyl), 2-propenyl (or allyl), 1-methylethenyl (or isopropenyl),2-methyl-2-propenyl, 2-methyl-1-propenyl, 2-butenyl and 3-butenyl.

As used herein, the term "catalyst" denotes any material which willactivate an aldehyde moiety and render it more susceptible tosubstitution. Among these catalysts are acidic halide Lewis acidcatalysts, Bronsted acid catalysts, acidic oxide catalysts, acidiccation exchange resin catalysts, and any organic or inorganic materialwhich is capable of partial hydrolysis in the reaction medium to formacidic conditions. Examples of catalysts are hydrobromic acid,hydrochloric acid, hydriodic acid, sulfuric acid, phosphoric acid,nitric acid, fluoroboric acid, perchloric acid, arylsulfonic acids andalkylsulfonic acids, for example, p-toluenesulfonic acid,methanesulfonic acid, formic acid, acetic acid, glycolic acid, lacticacid, propionic acid, monochloroacetic acid, dichloroacetic acid,trichloroacetic acid, trifluoroacetic acid, malonic acid, citric acid,fumaric acid, benzoic acid, salicylic acid, picric acid, trimelliticacid, aluminum chloride, ferric chloride, zinc chloride, stannicchloride, phosphorus trichloride, phosphorus pentachloride, borontrifluoride etherate, phosphorus oxychloride, thionyl chloride, ferricoxide, aluminum oxide, phosphorus pentaoxide, benzoyl chloride, benzoylperoxide, potassium fluoride, sulfonated coals, sulfonatedphenol-formaldehyde resins, sulfonated divinylbenzene cross linkedpolymers and exchangers with carboxyl group, phenol group oralumina-silicate skeleton. Further, the sulfinic acids which take partin the reaction may in some instances act as catalysts, thus alleviatingthe need to add a special catalyst to the reaction.

As used herein the term "reaction medium" denotes any non-solvent orsolvent capable of dispersing, partially dissolving or completelydissolving the reactants thus providing a fluid medium for thesereactants to interact forming the desired methanes. Examples of chemicalcompounds which may be utilized singly or in a combination as a"reaction medium" are methyl alcohol, ethyl alcohol, isopropyl alcohol,ethylene glycol, ethylene glycol monoethyl ether, propylene glycol,diethylene glycol, diethylene glycol dimethyl ether, toluene,chlorobenzene, 1-ethyl-2-methylindole, acetonitrile, ethylenedichloride, N,N-dimethylformamide, N,N-dimethylaniline, isopropyl crownether and water.

The novel compounds of Formula I, those of Formula XV, which encompassthe novel compounds of Formula XII and those of Formula XVI, hereinaboveare essentially colorless in the depicted form. When contacted with anacidic medium for example, silica gel or one of the types ordinarilyemployed in pressure-sensitive carbonless duplicating systems such assilton clay or phenolic resins, the compounds of Formulas I, XV, and XVIdevelop a yellow through bluish-red to reddish-violet colored image ofgood to excellent tinctorial strength, and possessing excellentxerographic copiability and enhanced solubility in common organicsolvents. The compounds are thus highly suitable for use as colorlessprecursors, that is, color-forming substances in pressure-sensitivecarbonless duplicating systems. The darker violet colors can be usedalone as color formers to produce images which are readily copiable,whereas the yellow, red and blue colors can be used as toners inadmixture with other color formers to produce images of a neutral shadewhich desirably are readily copiable by xerographic means.

The compounds of this invention may be incorporated in any of thecommercially accepted systems known in the carbonless duplicating art. Atypical technique for such application is as follows. Solutionscontaining one or more colorless precursor compounds of Formulas I, XVand XVI optionally in admixture with other color formers, in suitablesolvents are microencapsulated by well-known procedures for example asdescribed in U.S. Pat. Nos. 3,649,649, 3,429,827 and 4,000,087. Themicrocapsules are coated on the reverse side of a sheet with the aid ofa suitable binder and the coated transfer sheet is then assembled in amanifold with the microcapsule coated side in contact with a receivingsheet coated with an electron accepting substance, for example, siltonclay or a phenollic resin. Application of pressure to the manifold suchas that exerted by a stylus, typewriter or other form of writing orprinting causes the capsules on the reverse side to rupture. Thesolution of the color former released from the ruptured microcapsulesflows to the receiving sheet and on contact with the acidic mediumthereon forms yellow to reddish-violet colored images of good tinctorialstrength. It is, of course, obvious that variants of this mode ofapplication can be utilized. For example, the receiving sheet in amanifold can alternatively be coated with the subject compounds and theacidic developing agent can be contained in microcapsules applied to thereverse side of the top sheet in the manifold; or the receiving sheetcan be coated with a mixture containing both the acidic developing agentand the microencapsulated color former.

It has also been found that when the compounds of Formulas I, XV and XVIare intimately mixed with an acidic developer of the type generallyemployed in thermal papers such as described in U.S. Pat. No. 3,539,375,that is, papers which produce a colored image when contacted with aheated stylus or heated type, for example, bisphenol A, heating of themixture produces a colored image of varying shades from yellow toreddish-violet depending on the particular compound of the inventionemployed. The ability of the compounds of Formulas I, XV and XVI to forma deep color when heated in admixture with an acidic developer such asbisphenol A, makes them useful in thermal paper marking systems, eitherwhere an original or a duplicate copy is prepared by contacting thethermal paper with a heated stylus or heated type in any of the methodsgenerally known in the art.

The best mode contemplated by the inventors of carrying out thisinvention will now be described so as to enable any person skilled inthe art to which it pertains to make and use the same.

In accordance with one of the process aspects of this invention, the[(A)(1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)]methanes ofFormula I are obtained by interacting approximately equal molecularproportions of an appropriate aldehyde of the formula A-CHO with anappropriate 1-2-R² -5/6-R³ -indole and an appropriate R-phenylsulfinicacid wherein A, R, R¹, R² and R³ have the same respective meanings givenabove in relation to Formula I. Similarly, in accordance with a secondof the process aspects of this invention, the [(Q)(2-R⁵ -4-R⁶-phenyl)(R-phenylsulfonyl)]methanes of Formula XV are obtained byinteracting equal molecular proportions of the appropriate 2-R⁵ -4-R⁶-benzaldehyde with an appropriate compound of the formula Q-H and anappropriate R-phenylsulfinic acid. The definition of Q, R, R⁵ and R⁶ arethose given hereinabove in relation to Formula XV. In accordance withstill another process aspect of this invention the [(Z)(1-R⁸-2-pyrrolyl)(R-phenylsulfonyl)]methanes of Formula XVI are obtained byinteracting approximately equal molecular proportions of an appropriatealdehyde of the formula Z-CHO with an appropriate 1-R⁸ -pyrrole and anappropriate R-phenylsulfinic acid wherein Z, R and R⁸ have the samerespective meanings given above in relation to Formula XVI. Thesereactions are conveniently carried out in a reaction medium as listedhereinabove, for example, a lower hydrocarbon chain alcohol orN,N-dimethylformamide in the presence of a catalyst selected from thoselisted hereinabove, at a temperature in the range of 5° to 150° C. forapproximately one to thirty-five hours. The [(A)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methane of Formula I, the [(Q)(2-R⁵ -4-R⁶-phenyl)(R-phenylsulfonyl)]methane of Formula XV or the [(Z)(1-R⁸-2-pyrrolyl)(R-phenylsulfonyl)]methanes of Formula XVI thus obtained canbe isolated by filtration if the product is not soluble in the reactionmedium or by the addition of a basic substance, for example,triethanolamine or ammonium hydroxide to effect precipitation of themethane. Alternatively, the reaction mixture can be poured into water ora dilute aqueous base, for example, ammonium hydroxide and the methaneisolated by filtration or extracted with an organic solvent, forexample, chlorobenzene or toluene followed by evaporation of the organicsolvent leaving the product as a residue. The isolated methane can bepurified by conventional means such as trituration, recrystallization orreslurrying with a suitable organic liquid.

In accordance with a further process aspect of the present invention,the [α,ω-bis(1-R¹ -2-R² -5/6-R³-3-indolyl)-α,ω-bis(R-phenylsulfonyl)]alkanes of Formula XI can beprepared by interacting approximately two molecular proportions of a1-R¹ -2-R² -5/6-R³ -indole and approximately two molecular proportionsof a R-phenylsulfinic acid with approximately one molecular proportionof the appropriate aliphatic dialdehyde of the formula (CH₂)_(m) (CHO)₂,wherein R, R¹, R² and R³ each have the same respective meanings given inrelation to Formula XV. The reaction is conveniently carried out in amanner similar to that described above for the preparation of the[(A)(1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)]methanes ofFormula I and the product is isolated in a similar manner.

In accordance with a third of the process aspects of this invention, the[1,4-bis(1-R¹ -2-R² -5/6-R³-3-indolyl)-1,4-bis(R-phenylsulfonyl)]butanes of Formula XI can beprepared by interacting approximately two molecular proportions of a1-R¹ -2-R² -5/6-R³ -indole and approximately two molecular proportionsof a R-phenylsulfinic acid with approximately one molecular proportionof a 2,5-di(C₁ -C₃ alkoxy)tetrahydrofuran. The reaction is convenientlycarried out in a reaction medium selected from those listed hereinabovein the presence of a catalyst selected from those listed hereinabove,for example, hydrochloric acid in a temperature in the range of 5° to50° C. for approximately one hour to eighteen hours. The [1,4-bis(1-R¹-2-R² -5/6-R³ -3-indolyl)-1,4-bis(R-phenylsulfonyl)]butane thus obtainedcan be isolated by filtration.

The aliphatic, aromatic and heterocyclic aldehydes required as startingmaterials for the [(A)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methanes of Formula I, the[α,ω-bis(R-phenylsulfonyl)]alkanes of Formula XI, the [(Q)(2-R⁵ -4-R⁶-phenyl)(R-phenylsulfonyl)methanes of Formula XV and the [(Z)(1-R⁸-2-pyrrolyl)(R-phenylsulfonyl)methanes of Formula XVI constitute an oldand well-known class of compounds many of which are commerciallyavailable or are readily obtained by conventional syntheses well knownin the art. The following list of compounds exemplifies aliphatic,aromatic and heterocyclic aldehydes useful in carrying out the firststep of the processes of this invention leading to the compounds ofFormulas I, XI, XV and XVI.

Benzaldehyde,

2-Methylbenzaldehyde,

2-Chlorobenzaldehyde,

2-Methoxybenzaldehyde,

4-Methoxybenzaldehyde,

2-Bromobenzaldehyde,

4-Methylbenzaldehyde,

4-Chlorobenzaldehyde

2-Ethoxybenzaldehyde,

4-Ethoxybenzaldehyde,

2-Fluorobenzaldehyde,

4-Isopropylbenzaldehyde,

2,4-Dimethoxybenzaldehyde,

2-Chloro-4-dimethylaminobenzaldehyde,

3-Ethoxy-4-methoxybenzaldehyde,

2-Methoxy-4-dimethylaminobenzaldehyde,

2-Methoxy-4-diethylaminobenzaldehyde,

4-Dimethylaminobenzaldehyde,

4-Benzylaminobenzaldehyde,

5-methoxyindole-3-carboxaldehyde,

4-(N-Methylbenzylamino)benzaldehyde,

Indole-3-carboxaldehyde,

N-Methylpyrrole-2-carboxaldehyde,

2-Pyridinecarboxaldehyde,

3-Pyridinecarboxaldehyde,

4-Pyridinecarboxaldehyde,

Pyrrole-2-carboxaldehyde,

2-Thiophenecarboxaldehyde,

N-Ethyl-3-carbazolecarboxaldehyde,

2-Methyl-1-n-octylindole-3-carboxaldehyde,

1-n-Butyl-2-phenylindole-3-carboxaldehyde,

9-Formyljulolidine,

4-(N-Ethylbenzylamino)benzaldehyde,

1,2-Dimethylindole-3-carboxaldehyde,

1-Ethyl-2-phenylindole-3-carboxaldehyde,

4-Diethylaminobenzaldehyde,

2-Methyl-4-diethylaminobenzaldehyde,

1-Ethyl-2-methylindole-3-carboxaldehyde,

Formaldehyde,

Acetaldehyde,

Butylaldehyde,

Deconal,

Hexanal,

Heptaldehyde

Octyl aldehyde,

Propionaldehyde,

Valeraldehyde,

Glutaraldehyde, and

Nonyl aldehyde.

The indole compounds represented by 1-R¹ -2-R² -5/6-R³ -indole which arerequired to obtain the [(A)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methanes of Formula I and the[α,ω-bis(1-R¹ -2-R² -5/6-R³-3-indolyl)-α,ω-bis(R-phenylsulfonyl)]alkanes of Formula XI and thepyrrole compounds represented by 1-R⁸ -pyrrole which are required toobtain the [(Z)(1-R² -2-pyrrole)(R-phenylsulfonyl)]methanes of FormulaXVI form an old and well-known class of compounds readily obtained byconventional processes well known in the art. The following list ofcompounds exemplifies indole, pyrrole and carbazole compounds fallingwithin the ambit of the formula 1-R¹ -2-R² -5/6-R³ -indole, pyrrolecompounds falling within the ambit of the formula 1-R⁸ -pyrrole andcarbazole compounds falling within the ambit of the formula 9-R⁸-carbazole which are useful in the practice of the processes of thisinvention for producing the aforesaid methanes and alkanes of FormulasI, XI and XVI.

Indole

1-Methylindole,

2-Methylindole,

1,2-Dimethylindole,

1-Ethyl-2-methylindole,

2-Phenylindole,

1-Propyl-2-methylindole,

1-Benzyl-2-methylindole,

1-Butyl-2-methylindole,

1-Octyl-2-methylindole,

2-Ethyl-5-methylindole,

1-Benzyl-5-fluoroindole,

1-Methyl-6-nitroindole,

5-Methoxy-1-butylindole,

1-Allyl-2-methylindole,

1,2-Dimethyl-6-nitroindole,

1-(4-Chlorobenzyl)-2-methyl-5-nitroindole,

2-Ethylindole,

2-Ethyl-1-methylindole,

1-Isopropylindole,

2-Isopropylindole,

1-Methyl-5-bromo-6-nitroindole,

2,5,6-Trimethylindole,

1-Isobutyl-2-methylindole,

6-Bromo-2-methylindole,

1-Hexylindole,

1-(2,5-Dimethylbenzyl)-2-methylindole,

2-Propylindole,

6-Chloro-2-phenylindole,

1-(2-Ethylhexyl)-2-methylindole,

1-(2,6-Dichlorobenzyl)-2-methylindole,

1-Vinyl-2-methylindole,

2-Ethyl-6-methylindole,

6-Fluoro-1-benzylindole,

1(4-Bromobenzyl)-2-isopropylindole,

1-(3-Chlorobenzyl)-2-ethylindole,

5-Chloro-1-benzylindole,

1-(2-Fluorobenzyl)-2-methylindole,

5-Iodo-1-(1-methylhexyl)indole,

5,6-Dimethoxyindole,

1-(2-Methylbenzyl)-2-methylindole,

5,6-Dichloro-2-phenylindole,

1-Isoamylindole,

1-[3-(2-Methyl)-1-propenyl]-2-methoxyindole,

Pyrrole,

N-Methylpyrrole,

N-Ethylpyrrole,

N-Propylpyrrole,

N-Isopropylpyrrole,

N-Phenylpyrrole,

Carbazole,

9-Methylcarbazole,

9-Ethylcarbazole,

9-Propylcarbazole,

9-Isopropylcarbazole, and

9-Phenylcarbazole.

Benzenesulfinic acid and substituted benzenesulfinic acids required asintermediates for the methanes of Formulas I, XV and XVI and the alkanesof Formula XI form an old and well-known class of compounds. Further, itis well known in the art that sulfinic acids are unstable and can not bestored for periods of time. Generally speaking, the process aspects ofthis invention the sulfinic acid is generated in situ in the reactionmedium by acidifying an alkali metal, alkaline earth metal, or ammoniumsalt of the sulfinic acid with a catalyst. The alkali metal, alkalineearth metal, or ammonium salts are readily obtainable by conventionalprocedures well known in the art. For example, benzenesulfonyl chlorideis interacted with sodium sulfite and sodium bicarbonate in water toobtain the desired sodium benzenesulfinate, which per se is stable andcan be stored until needed for reactions. The benzenesulfonyl chloridesare readily available from the interaction of phosphorus oxychloride ona benzenesulfonic acid or a salt thereof. The following compounds areexemplary of benzenesulfonyl chlorides useful in the preparation ofthese intermediates.

Benzenesulfonyl chloride,

p-Toluenesulfonyl chloride,

p-Bromobenzenesulfonyl chloride,

p-Chlorobenzenesulfonyl chloride,

4-Chloro-3-nitrobenzenesulfonyl chloride,

2,5-Dichlorobenzenesulfonyl chloride,

3,4-Dichlorobenzenesulfonyl chloride,

2,4-Dimethylbenzenesulfonyl chloride,

2,5-Dimethylbenzenesulfonyl chloride,

2,4-Dinitrobenzenesulfonyl chloride,

p-Fluorobenzenesulfonyl chloride,

p-Iodobenzenesulfonyl chloride,

o-Nitrobenzenesulfonyl chloride,

m-Nitrobenzenesulfonyl chloride,

p-Nitrobenzenesulfonyl chloride,

4-Methoxybenzenesulfonyl chloride,

p-Acetamidobenzenesulfonyl chloride and

p-Dodecylbenzenesulfonyl chloride.

The aromatic and heterocyclic compounds represented by the formula Q-H,which are required for interaction with the 2-R⁵ -4-R⁶ -benzaldehydesand the R-phenylsulfinic acids to obtain the [(Q)(2-R⁵ -4-R⁶-phenyl)(R-phenylsulfonyl)]methanes of Formula XV form old and wellknown classes of compounds readily obtained by conventional procedureswell known in the art. The following list of compounds exemplifiesaromatic and heterocyclic compounds falling within the ambit of theformula Q-H which are useful in the practice of the process of thisinvention for producing the aforesaid methanes of Formula XV.

N-Benzyl-N-sec-butylaniline,

N,N-Di-sec-butylaniline,

N,N-Diethyl-3-isopropylaniline,

N,N-Diisobutylaniline,

N,N-Diethyl-3-propoxyaniline,

N,N-Dipropylaniline,

N-Isopropyl-N-methylaniline,

N-Methyl-N-propylaniline,

N,N,N',N'-Tetrabutyl-m-phenylenediamine,

N,N-Dipropyl-o-anisidine,

N-Isobutyl-N-ethylaniline,

N,N,N',N'-Tetraethyl-m-phenylenediamine,

N-Propyl-N-ethylaniline,

N,N-Diethyl-3-ethylaniline,

N-Benzyl-N-sec-butyl-3-propoxyaniline,

N,N-Dimethyl-m-toluidine,

Julolidine

N,N,N',N'-Tetramethyl-m-phenylenediamine,

N,N-Dibutylaniline,

N,N-Diethyl-3-ethoxyaniline,

N,N-Diethyl-m-anisidine,

N,N-Dimethylaniline,

N-Benzyl-N-ethylaniline,

N,N-Diethyl-m-toluidine

N,N-Diethylaniline,

N-Ethyl-N-methylaniline,

N-Benzyl-N-methylaniline,

N-Benzyl-N-propylaniline,

N,N-Dimethyl-3-bromoaniline,

N,N,N',N'-Tetraisopropyl-m-phenylenediamine,

N,N-Dibutyl-3-fluoroaniline,

N-Benzyl-N-methyl-3-ethylaniline,

N,N,N',N'-Tetra-sec-butyl-m-phenylenediamine,

N-Benzyl-N-butyl-3-iodoaniline, and

N,N-Diisopropyl-3-chloraniline.

It will, of course, be understood by those skilled in the art ofchemistry that the compounds of this invention may exist and may berepresented in at least two tautomeric forms, namely, either as sulfonesor as sulfinic acid esters. However, infrared and nuclear magneticresonance spectroscopic determinations have established that thestructure depicted by the formulas herein, namely, sulfones or sulfonylderivatives is the most likely form to exist from the conditions of thereactions described herein.

The molecular structures of the compounds of this invention wereassigned on the basis of the modes of synthesis and study of theirinfrared and nuclear magnetic resonance spectra.

The following examples will further illustrate the invention without,however, limiting it thereto. All melting points are uncorrected.

EXAMPLE 1

To a stirred mixture of 175.0 ml of ethyl alcohol, 27.5 ml ofconcentrated hydrochloric acid, 30.4 g (0.15 mole) of 86.4 percentsodium p-toluenesulfinate and 18.5 g (0.125 mole) ofp-dimethylaminobenzaldehyde chilled to approximately 5° C., there wasslowly added 19.5 g (0.113 mole) of 91.2 percent 1-ethyl-2-methylindole.The resulting mixture was stirred for approximately three and one halfhours at ambient temperature, during which period the color changed fromblue to yellow. The pH of the mixture was adjusted to approximately 8 bythe addition of 40.0 g of triethanolamine and, after stirringapproximately twenty minutes at room temperature, the temperature wasraised to and maintained at 55°-60° C. for approximately twenty minutes.After cooling to approximately 10° C., the separated pink solid wascollected by filtration and washed with 100.0 ml of cold ethyl alcohol.The solid was then suspended in a mixture of 350.0 ml of water and 10.0g of triethanolamine at ambient temperature for approximately thirtyminutes, collected by filtration and washed first with 150.0 ml of 3percent aqueous triethanolamine and finally with 150.0 ml of water.After drying in vacuo at 40° C., there was obtained 42.2 g of[(4-dimethylaminophenyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane(Formula II: R═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═R⁵ ═H; R⁶ ═N(CH₃)₂)which softened at 155° C. and melted at 159°-161° C.

Significant infrared maxima appeared at 1310 (SO₂ ; m) and 1145 (SO₂ ;m) cm⁻¹. The nuclear magnetic resonance spectral analysis was concordantwith the assigned structure.

A toluene solution of this product contacted with an acidic clay, silicagel or a phenolic resin developed a bluish-red colored image.

EXAMPLE 2

With stirring, 3.8 g (0.025 mole) of p-dimethylaminobenzaldehyde wasadded to a mixture of 5.0 ml of concentrated hydrochloric acid, 35.0 mlof ethyl alcohol, 9.6 g (0.03 mole) of 55.6 percent sodiump-toluenesulfinate and 2.9 g (0.025 mole) of 1,2-dimethylindole. Afterstirring approximately one hour with heating at 55°-60° C., theresultant mixture was cooled to approximately 40° C. and 25.0 ml ofethyl alcohol was added. Then, 300 ml of water and 200 g of ice wereslowly added to the mixture with stirring and the resulting solid wascollected by filtration and washed with water. The water-wet filter cakewas resuspended in 60.0 ml of chilled isopropyl alcohol and sufficientammonium hydroxide to maintain slightly alkaline conditions. Afterstirring for approximately forty-five minutes at 5°-10° C., thesuspended solid was recollected by filtration, washed with 15.0 ml offresh isopropyl alcohol and dried at 45° C. in vacuo to obtain 8.9 g of[(4-dimethylaminophenyl)(1,2-dimethyl-3-indolyl)(4-methylphenylsulfonyl)]methane(Formula II: R═4--CH₃ ; R¹ ═R² ═CH₃ ; R³ ═R⁵ ═H; R⁶ ═N(CH₃)₂), a palepink-violet colored compound which melted at 179°-181° C.

Significant infrared maxima appeared at 1305 (SO₂ ; w) and 1135 (SO₂ ;w) cm⁻¹. The nuclear magnetic resonance spectrum was concordant with theassigned structure.

A toluene solution of this product contacted with silica gel, acid clayor phenolic resin developed a bluish-pink colored image.

EXAMPLE 3

To a stirred mixture of 175.0 ml of ethyl alcohol, 30.35 g (0.14 mole)of 81.4 percent sodium p-toluenesulfinate, 19.5 g (0.112 mole) of 91.2percent 1-ethyl-2-methylindole and 5.5 g (0.125 mole) of acetaldehydeunder an atmosphere of nitrogen and maintaining the temperature atapproximately 5° C. by means of an ice-water bath, there was addeddropwise 27.5 ml of concentrated hydrochloric acid. After stirringapproximately four hours at ambient temperature, the white solid whichhad separated was collected by filtration, washed with a small amount ofethyl alcohol and air dried to a constant weight of 43.7 g. The solidwas dissolved in a hot mixture of ethyl and methyl alcohols, treatedwith 3.0 g of decolorizing charcoal, the solution filtered while hot,and then set aside at ambient temperature overnight. The resultingslurry was placed in a refrigerator for approximately two hours. Theseparated solid was then collected by filtration, washed with 500.0 mlof ethyl alcohol and air-dried to obtain 17.8 g of[(methyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane(Formula X: R═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═R⁴ ═H; n═1), a paleyellow solid which melted at 140°-142° C. developing a purple color.

Significant infrared maxima appeared at 1290 (SO₂ ; m) and 1138 (SO₂ ;m) cm⁻¹.

Anal. Calcd. for C₂₀ H₂₃ NO₂ S: C 70.38; H 6.75; N 4.11; S 9.38. Found:C 70.58; H 6.94; N 4.15; S 9.28.

The filtrate from the recrystallization above was concentrated toapproximately 500 ml, cooled, the solid collected by filtration anddried to obtain a second crop of 9.3 g of the product which melted overthe range 140°-151° C.

Significant infrared maxima appeared at 1290 (SO₂ ; m) and 1138 (SO₂ ;s) cm⁻¹.

An intimately ground mixture of 0.05 g of the product obtained in thisexample and 0.05 g of bisphenol A was slowly heated in a test tube. Acolor change from white to dark purple was observed as the mixturemelted over the range 140°-146° C.

EXAMPLE 4

A stirred mixture of 5.0 g (0.043 mole) of indole, 1.5 g (0.05 mole) ofp-formaldehyde, 7.65 g (0.043 mole) of sodium p-toluenesulfinate, 3.87ml of glacial acetic acid and 36.6 ml of N,N-dimethylformamide washeated at approximately 150° C. for approximately four hours. Theslightly cooled reaction mixture was then slowly poured with stirringinto approximately 110 ml of water and 75.0 ml of chlorobenzene wasadded. The layers were separated after approximately twenty minutes andthe water layer extracted a second time with 75.0 ml of freshchlorobenzene and separated. The organic extracts were combined, washedwith cold water and separated. A solid separated and was collected byfiltration from the combined chlorobenzene layers and dried to obtain2.18 g of [(3-indolyl)(4-methylphenylsulfonyl)]methane (Formula X:R═4--CH₃ ; R¹ ═R² ═R³ ═R⁴ ═H; n═0) as a white solid which melted at152°-153° C. developing a dark purple color.

The infrared spectrum had a significant maximum at 1142 (SO₂ ; m) cm⁻¹.The nuclear magnetic resonance spectrum was concordant with the assignedstructure.

An intimately ground mixture of this product with an equal weight ofbisphenol A thermally developed a deep purple color over the range150°-155° C.

EXAMPLE 5

To a stirred mixture at room temperature of 3.5 g (0.026 mole) of2,5-dimethoxytetrahydrofuran, 9 g (0.05 mole) of 89 percent1-ethyl-2-methylindole, 15 g (0.073 mole) of 86.4 percent sodiump-toluenesulfinate and 175.0 ml of ethyl alcohol, there was slowly added15.0 ml of concentrated hydrochloric acid. The mixture was stirred atroom temperature for approximately three hours and the solid that formedwas collected by filtration and washed with 200.0 ml of ethyl alcohol.After drying, there was obtained 17.9 g of[α,ω-bis(1-ethyl-2-methyl-3-indolyl)-α,ω-bis(4-methylphenylsulfonyl)]butane(Formula XI: R═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═H; m═2), an off-whitesolid which melted at 174°-175° C. developing a deep blue-black color.

In the infrared spectrum, significant maxima appeared at 1308 (SO₂ ; m)and 1142 (SO₂ ; m) cm⁻¹. The nuclear magnetic resonance spectrum wasconcordant with the assigned structure.

EXAMPLE 6

To a solution of 75.0 ml of ethyl alcohol and 39.1 g of 90 percentmethanesulfonic acid, there was slowly added at room temperature withstirring 25.1 g (0.12 mole) of 85 percent sodium p-toluenesulfinate,14.5 g (0.12 mole) of N,N-dimethylaniline and 14.9 g (1.0 mole) ofp-dimethylaminobenzaldehyde. The reaction mixture was then heated withstirring at reflux temperature for approximately twenty-four hours andwas then cooled to approximately 30° C. and 225.0 ml of ethyl alcohol,70.0 ml of water and 10.0 ml of glacial acetic acid were stirred intothe mixture. Then, 34.0 ml of concentrated ammonium hydroxide was slowlyadded allowing the temperature to rise to approximately 36° C. Aftercooling and stirring the mixture at approximately 5° C. for two hours,the solid which formed was collected by filtration and sequentiallywashed twice with 25.0 ml portions of 50 percent aqueous ethyl alcohol,three times with 100.0 ml portions of water and twice with 25.0 mlportions of 50 percent aqueous ethyl alcohol. After drying in vacuo,there was obtained 31.9 g of a light blue solid which melted over therange 140°-160° C. Twenty-five grams of the product obtained above waspurified by reslurrying in 80.0 ml of ethyl alcohol at approximately 55°C. for two hours. The slurry was cooled to room temperature, the solidcollected by filtration, washed twice with 25.0 ml portions of ethylalcohol and dried to obtain 20.7 g of[bis(4-dimethylaminophenyl)(4-methylphenylsulfonyl)]methane (Formula XV:R═4--CH₃ ; R⁵ ═H; R⁶ ═N(CH₃)₂ ; Q═4-(CH₃)₂ NC₆ H₄), a light blue solidwhich melted at 173°-175° C.

The infrared spectrum had significant maxima which appeared at 1145 (SO₂; s) and 1302 (SO₂ ; s) cm⁻¹. The nuclear magnetic resonance spectrumwas in accord with the assigned structure.

A toluene solution of the product contacted with an acidic claydeveloped a blue-colored image.

Proceeding in a manner similar to that described in Example 1 above,approximately equimolecular proportions of the appropriate aldehyde ofthe formula A-CHO, the appropriate 1-R¹ -2-R² -5/6-R³ -indole and theappropriate R-phenylsulfinic acid were interacted in ethyl alcohol inthe presence of hydrochloric acid to obtain the methanes of Formulas IIand V listed hereinbelow. The nuclear magentic resonance spectrum foreach of the methanes listed hereinbelow was in accord with the assignedstructure. A toluene solution of each product contacted with silica gel,acid clay and/or phenolic resin developed the indicated colored image.

EXAMPLE 7

Six and two-tenths grams of 80 percent sodium benzenesulfinate, 3.7 g ofp-dimethylaminobenzaldehyde and 3.8 g of 94.4 percent1-ethyl-2-methylindole were interacted at approximately 28° C. to obtain10.7 g of a methane of Formula II wherein R═R³ ═R⁵ ═H; R¹ ═C₂ H₅ ; R²═CH₃ ; R⁶ ═N(CH₃)₂, a solid which melted over the range of 148°-170° C.The infrared spectrum had a significant maxima which appeared at 1310(SO₂ ; m) cm⁻¹. This product developed a red violet colored image.

EXAMPLE 8

Six and three tenths grams of 85 percent sodium p-toluenesulfinate, 2.2g of 98 percent of N-methylpyrrole-2-carboxaldehyde and 3.8 g of 94percent 1-ethyl-2-methylindole were interacted in 35.0 ml to obtain 8.4g of a methane of Formula V wherein R═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═R⁸ ═CH₃ ;R³ ═H), a purple brown colored solid which melted at 180° C. Asignificant infrared maxima appeared at 1148 (SO₂ ; m) cm⁻¹ and thenuclear magnetic resonance spectrum was consistent with the assignedstructure. The product developed a yellow colored image.

Following a procedure similar to that described in Example 2 above,approximately equimolecular proportions of the appropriate aldehyde ofthe formula A-CHO, the appropriate 1-R¹ -2-R² -5/6-R³ -indole and theappropriate R-phenylsulfinic acid were interacted in ethyl alcohol inthe presence of hydrochloric acid to obtain the methanes of Formulas II,III, IV, VI, VII, VIII, and IX listed hereinbelow. The nuclear magneticresonance spectrum for each of the methanes listed hereinbelow wasconsistent with the assigned structure. A toluene solution of eachproduct contacted with silica gel, acid clay and/or phenolic resindeveloped the indicated colored image.

EXAMPLE 9

Nine and six tenths grams of 55.6 percent sodium p-toluenesulfinate, 3.4g of anisaldehyde and 3.8 g of 86.1 percent 1-ethyl-2-methylindole wereinteracted to obtain 9.4 g of a methane of Formula II wherein R═4--CH₃ ;R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═R⁵ ═H; R⁶ ═OCH₃, a pale orange solid whichmelted over the range 181°-184° C. Significant infrared maxima appearedat 1310 (SO₂ ; m) and 1140 (SO₂ ; w) cm⁻¹. The product developed a paleyellow colored image.

EXAMPLE 10

Six and one half grams of 81.9 percent sodium p-toluenesulfinate, 5.1 gof 95 percent 2-phenylindole and 3.8 g of p-dimethylaminobenzaldehydewere interacted to obtain 10.3 g of a methane of Formula II whereinR═4--CH₃ ; R¹ ═R³ ═R⁵ ═H; R² ═C₆ H₅ ; R⁶ ═N(CH₃)₂, a light brown powdermelting at 185.5°-188° C. The infrared spectrum had significant maximaat 1310 (SO₂ ; m) and 1140 (SO₂ ; m) cm⁻¹. The product developed aviolet colored image.

EXAMPLE 11

Six and one half grams of 81.9 percent sodium p-toluenesulfinate, 3.0 gof indole and 3.8 g of p-dimethylaminobenzaldehyde were interacted toobtain 2.2 g of a methane of Formula II wherein R═4--CH₃ ; R¹ ═R² ═R³═R⁵ ═H; R⁶ ═N(CH₃)₂, a pale brown solid which melted at 167°-169° C. Asignificant infrared maximum appeared at 1140 (SO₂ ; m) cm⁻¹. Theproduct developed a violet-pink colored image.

EXAMPLE 12

Three and seven tenths grams of 81.9 percent sodium p-toluenesulfinate,2.1 g of 2,5-dimethylindole and 2.1 g of p-dimethylaminobenzaldehydewere interacted to obtain 6.5 g of a methane of Formula II whereinR═4--CH₃ ; R¹ ═R⁵ ═H; R² ═R³ ═CH₃ ; R⁶ ═N(CH₃)₂, a solid which meltedover the range 106°-112° C. In the infrared spectrum, significant maximaappeared at 1305 (SO₂ ; m) and 1145 (SO₂ ; m) cm⁻¹. The productdeveloped a pink colored image.

EXAMPLE 13

Six and one half grams of 81.9 percent sodium p-toluenesulfinate, 3.6 gof 97 percent p-chlorobenzaldehyde and 3.8 g of 1-ethyl-2-methylindolewere interacted to obtain 4.0 g of a methane of Formula II whereinR═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═R⁵ ═H; R⁶ ═Cl, a solid which meltedat 146°-149° C. Significant infrared maxima appeared at 1305 (SO₂ ; m)and 1144 (SO₂ ; b) cm⁻¹. The product developed a yellow colored image.

EXAMPLE 14

Six and one half grams of 81.9 percent sodium p-toluenesulfinate, 3.0 gof p-tolualdehyde and 3.8 g of 86.1 percent 1-ethyl-2-methylindole wereinteracted to obtain 7.7 g of a methane of Formula II wherein R═4--CH₃ ;R¹ ═C₂ H₅ ; R² ═R⁶ ═CH₃ ; R³ ═R⁵ ═H, a solid which melted at 138°-141°C. In the infrared spectrum, significant maxima appeared at 1305 (SO₂ ;m) and 1145 (SO₂ ; m) cm⁻¹. The product developed a yellow-green coloredimage.

EXAMPLE 15

Six and one half grams of 81.9 percent sodium p-toluenesulfinate, 6.3 gof 95 percent 4-(N-ethyl-N-benzyl)benzaldehyde and 3.8 g of 86.1 percentof 1-ethyl-2-methylindole were interacted to obtain 15.3 g of a methaneof Formula II wherein R═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═R⁵ ═H; R⁶═N[(C₂ H₅)(CH₂ C₆ H₅)], a gray tar-like product. A significant infraredmaximum appeared at 1145 (SO₂ ; m) cm⁻¹. The product developed ared-violet colored image.

EXAMPLE 16

Six and one half grams of 81.9 percent sodium p-toluenesulfinate, 5.6 gof N-ethyl-3-carbazolecarboxaldehyde and 3.8 g of 86.1 percent1-ethyl-2-methylindole were interacted to obtain 10.8 g of a methane ofFormula IV wherein R═4--CH₃ ; R¹ ═R⁷ ═C₂ H₅ ; R² ═CH₃ ; R³ ═H, a magentacolored solid which melted at 168°-171° C. A significant infrared maximaappeared at 1300 (SO₂ ; m) and 1140 (SO₂ ; m) cm⁻¹. The productdeveloped a violet-pink colored image.

EXAMPLE 17

Six and one half grams of 81.9 percent sodium p-toluenesulfinate, 5.0 gof julolidinealdehyde and 3.8 g of 86.1 percent 1-ethyl-2-methylindolewere interacted to obtain 12.9 g of a methane of Formula IX whereinR═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═H, a blue colored solid. Theinfrared spectrum showed a maximum at 1145 (SO₂ ; m) cm⁻¹. The productdeveloped a light purple colored image.

EXAMPLE 18

Six and one half grams of 81.9 percent sodium p-toluenesulfinate, 2.4 gof 2-furaldehyde and 3.8 g of 86.1 percent 1-ethyl-2-methylindole wereinteracted to obtain 4.5 g of a methane of Formula VI wherein R═4--CH₃ ;R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═H, a black solid which melted at 144°-146° C.A significant infrared maxima appeared at 1305 (SO₂ ; m) and 1150 (SO₂ ;m) cm⁻¹. The product developed a yellow colored image.

EXAMPLE 19

Six and two tenths grams of 85.9 percent sodium p-toluenesulfinate, 4.5g of 94.4 percent 1-ethyl-2-methylindole and 2.8 g ofthiophene-2-carboxaldehyde were interacted to obtain 10.0 g of methaneof Formula VII wherein R═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═H, a whitesolid which melted at 168°-169° C. with decomposition. The infraredspectrum showed a significant maximum at 1140 (SO₂ ; m) cm⁻¹. Theproduct developed a yellow colored image.

EXAMPLE 20

Six and four tenths grams of 85 percent sodium p-toluenesulfinate, 2.7 gof 2-pyridine carboxaldehyde and 4.2 g of 94.4 percent1-ethyl-2-methylindole were interacted at room temperature to obtain 6.2g of a methane of Formula VIII wherein R═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ;R³ ═H, a slightly pink colored solid which melted at 180°-182° C. Asignificant infrared maximum appeared at 1140 (SO₂ ; m) cm⁻¹. Theproduct slowly developed a purple-red colored image.

EXAMPLE 21

Six and one half grams of 85.9 percent sodium p-toluenesulfinate, 4.6 gof 1-ethyl-2-methylindole-3-carboxaldehyde and 3.8 g of1-ethyl-2-methylindole were interacted to obtain 4.5 g of a methane ofFormula III wherein R═4--CH₃ ; R¹ ═R^(1') ═C₂ H₅ ; R² ═R^(2') ═CH₃ ; R³═R^(3') ═H, a pink colored solid which melted over the range 146°-152°C. The infrared spectrum had significant maxima at 1305 (SO₂ ; m) and1150 (SO₂ ; m) cm⁻¹. The product developed a deep orange colored image.

EXAMPLE 22

Six and one half grams of 85.9 percent sodium p-toluenesulfinate, 3.6 gof indole-3-carboxaldehyde and 4.1 g of 1-ethyl-2-methylindole wereinteracted at ambient temperature to obtain 5.8 g of a methane ofFormula III wherein R═4--CH₃ ; R² ═C₂ H₅ ; R¹ ═CH₃ ; R³ ═R^(1') ═R^(2')═R^(3') ═H, a pink colored solid which melted over the range 190°-210°C. The infrared spectrum had significant maxima at 1280 (SO₂ ; m) and1135 (SO₂ ; m) cm⁻¹. The product developed a deep orange colored image.

In a manner similar to that described in Example 3 above, approximatelyequimolecular proportions of the appropriate aldehyde of the formulaA--CHO, the appropriate 1-R¹ -2-R² -5/6-R³ -indole and the appropriateR-phenylsulfinic acid were interacted in ethyl alcohol in the presenceof hydrochloric acid to obtain the methanes or alkanes of Formulas II,V, VI, VII, X and XI listed hereinbelow. The nuclear magnetic resonancespectrum for each of the methanes listed hereinbelow was in accord withthe assigned structure.

EXAMPLE 23

Eight grams of 1,2-dimethylindole, 2.5 g of acetaldehyde and 15 g of86.4 percent sodium p-toluenesulfinate were interacted to obtain 11.2 gof a methane of Formula X wherein R═4--CH₃ ; R¹ ═R² ═CH₃ ; R³ ═R⁴ ═H;n=1, a white solid which melted at 166°-167° C. developing a deep purplecolor. The infrared spectrum showed significant maxima at 1300 (SO₂ ; b)and 1145 (SO₂ ; m) cm⁻¹.

EXAMPLE 24

Ten and one half grams of 2-phenylindole, 2.5 g of acetaldehyde and 15 gof 86.4 percent sodium p-toluenesulfinate were interacted to obtain 12.6g of a methane of Formula X wherein R═4--CH₃ ; R¹ ═R³ ═R⁴ ═H; R² ═C₆ H₅; n=1, a gray solid which melted at 172°-174° C. with decompositiondeveloping a blue color. Significant infrared spectrum maxima appearedat 1300 (SO₂ ; m) and 1145 (SO₂ ; m) cm⁻¹.

EXAMPLE 25

Thirty and thirty-five one hundredths grams of 86.4 percent sodiump-toluenesulfinate, 11.6 g of indole and 5.5 g of acetaldehyde wereinteracted to obtain 27.35 g of a methane of Formula X wherein R═4--CH₃; R¹ ═R² ═R³ ═R⁴ ═H; n=1, a pink-salmon colored solid which melted at160°-162° C. developing a dark red color. The infrared spectrum showedsignificant maxima at 1290 (SO₂ ; m) and 1141 (SO₂ ; m) cm⁻¹. Anintimately ground mixture of the product with an equal weight ofbisphenol A thermally developed a deep red color at 160°-162° C.

EXAMPLE 26

Six and seven one hundredths grams of 86.4 percent sodiump-toluenesulfinate, 3.9 g of 91.2 percent 1-ethyl-2-methylindole and2.85 g of heptaldehyde were interacted to obtain 4.8 g of a methane ofFormula X wherein R═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═R⁴ ═CH₃ ; R³ ═H; n=5, anoily orange solid. Significant infrared maxima appeared at 1315 (SO₂ ;m) and 1148 (SO₂ ; m) cm⁻¹. The product combined with an equal weight ofbisphenol A in intimately ground admixture thermally developed a deepred color.

EXAMPLE 27

Two and one half grams of glutaraldehyde, 8 g of 1-ethyl-2-methylindoleand 12 g of 86.4 percent sodium p-toluenesulfinate were interacted atambient temperature to obtain 6.5 g of a methane of Formula XI whereinR═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═H; m=3, a light tan solid which,after one recrystallization from ethyl alcohol, melted at 169°-170° C.developing a deep purple color. Significant infrared maxima appeared at1300 (SO₂ ; m) and 1145 (SO₂ ; m) cm⁻¹.

EXAMPLE 28

One and seven tenths grams of 2-pyridine carboxaldehyde, 2.8 g of1-ethyl-2-methylindole and 3.0 g of 4-acetamidobenzenesulfinic acid wereinteracted in the absence of hydrochloric acid to obtain 5.5 g of amethane of Formula VIII wherein R═CH₃ CONH; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═H,a white solid which melted at 214.8°-215.9° C. A significant infraredmaximum appeared at 1320 (SO₂ ; m) cm⁻¹. A toluene solution of theproduct contacted with an acidic clay developed a yellow colored image.

EXAMPLE 29

Two and one half grams of N-methylpyrrole, 5.6 g of1-ethyl-2-methylindole-3-carboxaldehyde and 6.0 g of sodiump-toluenesulfinate were interacted to obtain 7.1 g of a methane ofFormula V wherein R═R³ ═CH₃ ; R¹ ═C₂ H₅ ; R⁷ ═CH₃, a pink solid whichmelted at 175.5°-176.5° C. A significant infrared maximum appeared at1302 (SO₂ ; m) cm⁻¹. A toluene solution of the product contacted withsilica gel, an acidic clay or a phenolic resin developed a yellowcolored image.

EXAMPLE 30

Five and six tenths grams of 2-thienylcarboxaldehyde, 9.2 g of 86.1percent 1-ethyl-2-methylindole and 8.2 g of sodium benzenesulfinate wereinteracted to obtain 0.8 g of a methane of Formula VII R═R³ ═H; R¹ ═C₂H₅ ; R² ═CH₃, a red-violet colored solid which melted at 119.5°-124° C.The infrared spectrum showed a significant maximum at 1300 (SO₂ ; m)cm⁻¹. A toluene solution of the product contacted with an acidic clay orsilica gel developed a deep yellow colored image.

EXAMPLE 31

Four and eight tenths grams of furfural, 9.2 g of 86.1 percent1-ethyl-2-methylindole and 8.2 g of sodium benzenesulfinate wereinteracted to obtain 2.1 g of a methane of Formula VI wherein R═R³ ═H;R¹ ═C₂ H₅ ; R² ═CH₃, a red-purple solid which melted at 123.5°-125° C.Significant infrared maxima appeared at 1300 (SO₂ ; s) and 1145 (SO₂ ;m) cm⁻¹. A toluene solution of the product contacted with silica gel, anacidic clay and a phenolic resin developed a yellow colored image.

EXAMPLE 32

One and one half grams of 2-thienylcarboxaldehyde, 3.0 g of 85.6 percent1-ethyl-2-methylindole and 3.0 g of magnesium 4-chlorobenzenesulfinatewere interacted to obtain 4.5 g of a methane of Formula VII whereinR═4--Cl; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═H, a pale pink colored solid whichmelted at 130°-135° C. The infrared spectrum showed a maximum at 1310(SO₂ ; m) cm⁻¹. A toluene solution of the product contacted with silicagel developed a yellow colored image.

EXAMPLE 33

Two and three tenths grams of 2-thienylcarboxaldehyde, 4.3 g of1-ethyl-2-methylindole and 3.5 g of 4-methoxybenzenesulfinic acid wereinteracted in methyl alcohol in the place of ethyl alcohol and in theabsence of hydrochloric acid to obtain 6.5 g of a methane of Formula VIIwherein R═4--OCH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═H, a white solid whichmelted at 150°-151° C. The infrared spectrum showed a maximum at 1305(SO₂ ; m) cm⁻¹. A toluene solution of the product when spotted on silicagel as an acidic clay developed a yellow colored image.

EXAMPLE 34

One and one half grams of 1,2-dimethylindole, 1.4 g ofp-dimethylaminobenzaldehyde and 1.4 g of freshly preparedp-methoxybenzenesulfinic acid were interacted in the absence ofhydrochloric acid at room temperature to obtain 2.0 g of a methane ofFormula II wherein R═4--OCH₃ ; R¹ ═R² ═CH₃ ; R³ ═R⁵ ═H, R⁶ ═N(CH₃)₂, apale pink colored solid which melted at 163°-166° C. Significantinfrared maxima appeared at 1305 (SO₂ ; w) and 1300 (SO₂ ; w) cm⁻¹. Atoluene solution of this product contacted with silica gel, acid clay orphenolic resin developed a bluish-red colored image.

Proceeding in a manner similar to that described in Example 4 above,approximately equimolecular proportions of the appropriate aldehyde ofthe formula A--CHO, the appropriate 1-R¹ -2-R² -5/6-R³ -indole and theappropriate R-phenylsulfinic acid were interacted in ethyl alcohol inthe presence of hydrochloric acid to obtain the methanes of Formulas IIand VII listed hereinbelow. The nuclear magnetic resonance spectrum foreach of the methanes listed hereinbelow was consistent with the assignedstructure. A toluene solution of each product contacted with silica gel,an acidic clay and/or a phenolic resin developed the indicated coloredimage.

EXAMPLE 35

One and eight tenths grams of p-diethylaminobenzaldehyde, 1.8 g of 85.6percent 1-ethyl-2-methylindole and 2.0 g of magnesium p-chlorobenzenesulfinate were interacted to obtain 4.5 g of a methane of Formula IIwherein R═4--Cl; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═R⁵ ═H; R⁶ ═N(C₂ H₅)₂, a pinkoil. In the infrared spectrum, a maximum appeared at 1270 (SO₂ ; m)cm⁻¹. The product developed a red colored image.

EXAMPLE 36

Two and three tenths grams of p-dimethylaminobenzaldehyde, 2.8 g of 85.6percent 1-ethyl-2-methylindole and 5.0 g of sodiump-dodecylbenzenesulfinate were interacted to obtain after extractionwith toluene followed by extraction with isopropanol 0.7 g of a methaneof Formula II wherein R═4--C₁₂ H₂₅ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═R⁵ ═H; R⁶═N(CH₃)₂, an oily solid. The nuclear magnetic resonance spectrum wasconcordant with the assigned structure. The product developed a blue-redcolored image.

EXAMPLE 37

Two and one half grams of 2-thienylcarboxaldehyde, 3.0 g of1-ethyl-2-methylindole and 5.0 g of sodium p-dodecylbenzenesulfinatewere interacted to obtain, after extracting with toluene, 2.3 g of amethane of Formula VII wherein R═4--C₁₂ H₂₅ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³═H, an oily solid which melted over the range 152.8°-162.5° C. Theinfrared spectrum had a significant maximum at 1180 (SO₂ ; m) cm⁻¹. Theproduct developed a yellow colored image.

Following a procedure similar to that described in Example 6 above,approximately equimolecular proportions of the appropriate 2-R⁵ -4-R⁶-benzaldehyde, the appropriate compound of the formula Q-H and theappropriate R-phenylsulfinic acid were interacted in ethyl alcohol toobtain the methanes of Formulas II and XV listed hereinbelow. Thenuclear magnetic resonance spectrum for each of the methanes listedhereinbelow was concordant with the assigned structure. A toluenesolution of each product contacted with silica gel, an acidic clayand/or a phenolic resin developed the indicated colored image.

EXAMPLE 38

Twenty and six tenths grams of 86.4 percent sodium p-toluenesulfinate,21.3 g of 99.2 percent N-ethyl-N-benzylaniline and 14.9 g ofp-dimethylaminobenzaldehyde were interacted in the presence of 36.4 g of95 percent methanesulfonic acid to obtain 28.7 g of a methane of FormulaXV wherein R═4--CH₃ ; R⁵ ═H; R⁶ ═N(CH₃)₂ ; Q═4--[(C₂ H₅)(C₆ H₅ CH₂)]NC₆H₄, a bluish-gray solid which melted over the range 166°-172° C. Asignificant infrared maximum appeared at 1148 (SO₂ ; m) cm⁻¹. Theproduct developed a blue colored image.

EXAMPLE 39

Twenty and six tenths grams of 86.4 percent sodium p-toluenesulfinate,21.3 g of 90 percent N,N-diethyl-3-ethoxyaniline and 14.9 g of4-dimethylaminobenzaldehyde were interacted in the presence of 36.4 g of95 percent methanesulfonic acid to obtain 5.4 g of a methane of FormulaXV wherein R═4--CH₃ ; R⁵ ═C₂ H₅ O; R⁶ ═N(C₂ H₅)₂ ; Q═4--(CH₃)₂ NC₆ H₄, alight tan colored solid which melted at 130°-132° C. The infraredspectrum had a significant maximum at 1144 (SO₂ ; m) cm⁻¹. The productdeveloped a blue-violet colored image.

EXAMPLE 40

Ten and three tenths grams of 86.4 percent sodium p-toluenesulfinate,10.7 g of 90.7 percent N,N-diethyl-3-ethoxyaniline and 12 g of4-(N-ethyl-N-benzyl)-aminobenzaldehyde were interacted in the presenceof 18.2 g of 95 percent methanesulfonic acid to obtain a methane ofFormula XV wherein R═4--CH₃ ; R⁵ ═C₂ H₅ O; R⁶ ═N(C₂ H₅)₂ ; Q═4--[(C₂H₅)(C₆ H₅ CH₂)NC₆ H₄ ], an oil. A significant infrared maximum appearedat 1145 (SO₂ ; s) cm⁻¹. The product developed a violet colored image.

EXAMPLE 41

Fourteen and nine tenths grams of 4-dimethylaminobenzaldehyde, 20.6 g of86.4 percent sodium p-toluenesulfinate and 16.0 g ofN,N-diethyl-3-methylaniline were interacted in the presence of 36.4 g of95 percent methanesulfonic acid to obtain 0.82 g of a methane of FormulaXV wherein R═4--CH₃ ; R⁵ ═CH₃ ; R⁶ ═N(C₂ H₅)₂ ; Q═4--(CH₃)₂ NC₆ H₄, adark brown oil. The infrared spectrum had a significant maximum at 1147(SO₂ ; m) cm⁻¹. The product developed a blue colored image.

EXAMPLE 42

Fourteen and nine tenths grams of 4-dimethylaminobenzaldehyde, 20.7 g of85.9 percent sodium p-toluenesulfinate and 14.7 g of N,N-diethylanilinewere interacted in 100.0 ml of isopropyl alcohol in place of ethylalcohol and in the presence of 29.0 ml of concentrated hydrochloric acidto obtain 0.82 g of a methane of Formula XV wherein R═4--CH₃ ; R⁵ ═H; R⁶═N(CH₃)₂ ; Q═4--(C₂ H₅)₂ NC₆ H₄, a gray solid which melted over therange 108°-150° C. The infrared spectrum had a significant maximum at1143 (SO₂ ; m) cm⁻¹. The product developed a blue colored image.

EXAMPLE 43

Eighteen and six tenths grams of 95.8 percent sodium p-toluenesulfinate,12.1 g of N,N-dimethylaniline and 18.6 g of2-chloro-4-dimethylaminobenzaldehyde were interacted in the presence of36.4 g of 95 percent methanesulfonic acid to obtain 2.7 g of a methaneof Formula XV wherein R═4--CH₃ ; R⁵ ═Cl; R⁶ ═N(CH₃)₂ ; Q═4--(CH₃)₂ NC₆H₄, pink colored solid which melted over the range 130.5°-146° C.Significant infrared maxima appeared at 1150 (SO₂ ; s) and 1305 (SO₂ ;m) cm⁻¹. The product developed a blue colored image.

EXAMPLE 44

Twenty and six tenths grams of 86.4 percent sodium p-toluenesulfinate,21.3 g of 3-ethoxy-N,N-diethylaniline and 13.6 g of p-anisaldehyde wereinteracted in the presence of 36.4 g of 95 percent methanesulfonic acidto obtain 13.8 g of a methane of Formula XV wherein R═4--CH₃ ; R⁵ ═H; R⁶═OCH₃ ; Q═2--C₂ H₅ O--4--(C₂ H₅)₂ NC₆ H₃, an off-white colored solidwhich melted at 117.2°-117.8° C. The infrared spectrum showedsignificant maxima at 1151 (SO₂ ; s) and 1304 (SO₂ ; s) cm⁻¹. Theproduct developed a yellow colored image.

EXAMPLE 45

Twenty and six tenths grams of 86.4 percent sodium p-toluenesulfinate,21.3 g of 90.7 percent N,N-diethyl-m-phenetidine and 12.0 g of4-methylbenzaldehyde were interacted in the presence of 36.4 g of 95percent methanesulfonic acid to obtain 23.9 g of a methane of Formula XVwherein R═4--CH₃ ; R⁵ ═H; R⁶ ═CH₃ ; Q═2--C₂ H₅ O--4--(C₂ H₅)₂ NC₆ H₃, awhite solid which melted at 108.4°-109.8° C. Significant infrared maximaappeared at 1143 (SO₂ ; s) and 1303 (SO₂ ; m) cm⁻¹. The productdeveloped a yellow colored image.

EXAMPLE 46

Eighteen and six tenths grams of 95.8 percent sodium p-toluenesulfinate,14.9 g of 4-dimethylaminobenzaldehyde and 17.7 g of 98 percentjulolidine were interacted in the presence of 29.5 ml of 37.9 percenthydrochloric acid to obtain 15.0 g of a methane of Formula XV whereinR═4--CH₃ ; R⁵ ═H; R⁶ ═N(CH₃)₂ ; Q=9-julolidinyl, a white solid whichmelted over the range 129.1°-134.4° C. The infrared spectrum showedsignificant maxima at 1140 (SO₂ ; s) and 1305 (SO₂ ; m) cm⁻¹.

EXAMPLE 47

Four and seven tenths grams of p-dimethylaminobenzaldehyde, 5.5 g of1-ethyl-2-methylindole and 8.0 g of 75 percent4-acetamidobenzenesulfinic acid were interacted to obtain afterreslurrying in isopropanol and filtering, 6.3 g of a methane of FormulaII wherein R═4--NHCOCH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═R⁵ ═H; R⁶ ═N(CH₃)₂,a solid which melted over the range 145°-157° C. The infrared spectrumshowed a maximum at 1165 (SO₂ ; m) cm⁻¹. The product developed ayellow-green colored image.

EXAMPLE 48

Fourteen and eight tenths grams of 99.4 percent N-ethyl-N-benzylaniline,10.4 g of p-dimethylaminobenzaldehyde and 11.4 g of sodiumbenzenesulfinate were interacted in the presence of 26.0 g ofmethanesulfonic acid to obtain 1.3 g of a methane of Formula XV whereinR═R⁵ ═H; R⁶ ═N(CH₃)₂ ; Q═4-[(C₂ H₅)--(C₆ H₅ CH₂)]NC₆ H₄, which meltedover the range 111°-118° C. A significant infrared maximum appeared at1300 (SO₂ ; m) cm⁻¹. The product developed a blue colored image.

Proceeding in a manner similar to that described in Example 6 above,approximately equimolecular proportions of 1-methylpyrrole, theappropriate aldehyde of the formula Z-CHO and the appropriateR-phenylsulfinic acid were interacted in ethyl alcohol in the presenceof hydrochloric acid to obtain the methanes of Formula XVI listedhereinbelow. The nuclear magnetic resonance spectrum for each of themethanes listed hereinbelow was in accord with the assigned structure. Atoluene solution of each product contacted with silica gel and/or anacidic clay developed the indicated colored image.

EXAMPLE 49

Four and two tenths grams of 4-chlorobenzaldehyde, 2.4 g of1-methylpyrrole and 6.0 g of sodium p-toluenesulfinate were interactedto obtain 7.3 g of a methane of Formula XVII wherein R═4--CH₃ ; R⁸ ═CH₃; R⁵ ═H; R⁶ ═Cl, a solid which melted at 122° C. with decomposition. Theinfrared spectrum had a significant maximum at 1305 (SO₂ ; m) cm⁻¹. Theproduct developed a yellow colored image.

EXAMPLE 50

Six grams of 4-methylbenzaldehyde, 4.2 ml of 1-methylpyrrole and 9.5 gof sodium p-toluenesulfinate were interacted to obtain 17.1 g of amethane of Formula XVII wherein R═4--CH₃ ; R⁶ ═R⁸ ═CH₃ ; R⁵ ═H, a pinkcolored solid which melted at 78° C. with decomposition. The infraredspectrum had a significant maximum at 1305 (SO₂ ; m) cm⁻¹. The productdeveloped a yellow color.

EXAMPLE 51

Seven and four tenths grams of 4-methoxybenzaldehyde, 4.5 g of1-methylpyrrole and 10.0 g of sodium benzenesulfinate were interacted toobtain 12.0 g of a methane of Formula XVII wherein R═R⁵ ═H; R⁶ ═CH₃ O;R⁸ ═CH₃, a pink colored solid which melted at 103.5°-105° C. Theinfrared spectrum had a significant maximum at 1305 (SO₂ ; m) cm⁻¹. Theproduct developed a yellow colored image.

EXAMPLE 52

Thirty-seven grams of 4-methoxybenzaldehyde, 44.5 g ofp-toluenesulfinate and 22.5 g of 1-methylpyrrole were interacted toobtain after extraction with 10 percent diethanolamine in isopropylalcohol 57.8 g of a methane of Formula XVII wherein R═4--CH₃ ; R⁸ ═CH₃ ;R⁵ ═H; R⁶ ═CH₃ O, a solid. The infrared spectrum had a significantmaximum at 1307 (SO₂ ; m) cm⁻¹. The product developed a yellow coloredimage.

EXAMPLE 53

Six and one half grams of 4-acetamidobenzenesulfinic acid, 2.5 g of1-methylpyrrol and 3.4 g of 2-thiophene-carboxaldehyde were interactedto obtain 3.2 g of a methane of Formula XVIII wherein R═4--NHCOCH₃ ; R⁸═CH₃, a rust colored solid which melted over the range 130°-145° C. Theinfrared spectrum had a significant maximum at 1305 (SO₂ ; m) cm⁻¹. Theproduct developed a pink colored image.

EXAMPLE 54

Seven grams of sodium benzenesulfinate, 3.4 g of2-thiophenecarboxaldehyde and 2.5 g of 1-methylpyrrole were interactedto obtain 3.0 g of a methane of Formula XVIII wherein R═H; R⁸ ═CH₃, apink colored solid which melted at 100°-102° C. The infrared spectrumhad a significant maximum at 1300 (SO₂ ; m) cm⁻¹. The product developeda yellow colored image.

EXAMPLE 55

Six grams of 98.5 percent sodium p-toluenesulfinate, 3.4 g of2-thiophenecarboxaldehyde and 2.5 g of 1-methylpyrrole were interactedto obtain after washing with 5 percent diethanolamine in isopropylalcohol 2.4 g of a methane of Formula XVIII wherein R═4--CH₃ ; R⁸ ═CH₃,a pink-white colored solid which melted at 118° C. with decomposition.The infrared spectrum had a significant maximum at 1305 (SO₂ ; m) cm⁻¹.The product developed a yellow colored image.

EXAMPLE 56

Nineteen grams of sodium p-toluenesulfinate, 9.6 g of 2-furaldehyde and8.5 g of 1-methylpyrrole were interacted to obtain 21.0 g of a methaneof Formula XIX wherein R═4--CH₃ ; R⁸ ═CH₃, a light gray colored solidwhich melted over the range 95°-100° C. The infrared spectrum had asignificant maximum at 1300 (SO₂ ; m) cm⁻¹. The product developed ayellow colored image.

EXAMPLE 57

Two grams of sodim p-toluenesulfinate, 2.4 g ofN-ethyl-3-carbazolecarboxaldehyde and 0.9 g of 1-methylpyrrole wereinteracted to obtain 3.0 g of a methane of Formula XX wherein R═4--CH₃ ;R⁷ ═C₂ H₅ ; R⁸ ═CH₃, a pale grape colored solid which melted over therange 82°-87° C. The infrared spectrum had a significant maximum at 1305(SO₂ ; m) cm⁻¹. The product developed a grape colored image.

Proceeding in a manner similar to that described in Example 1 abovesubstituting for ethyl alcohol and the concentrated hydrochloric acidthe appropriate reaction medium and the appropriate catalyst listed inExamples 58-82 of Table A hereinbelow, 4-dimethylaminobenzaldehyde,sodium p-toluenesulfinate and 1-ethyl-2-methylindole were interacted atthe indicated temperature to obtain a methane of Formula II whereinR═4--CH₃ ; R¹ ═C₂ H₅ ; R² ═CH₃ ; R³ ═R⁵ ═H; R⁶ ═N(CH₃)₂. A toluene oracetone solution of the product from Examples 58-82 contacted withsilica gel developed a blue-red colored image.

                  TABLE A                                                         ______________________________________                                        Ex-                               Reaction                                    ample Reaction Medium                                                                             Catalyst      Temperature                                 ______________________________________                                        58    ethylene dichloride                                                                         p-toluenesulfonic                                                                           25° C.                                                   acid                                                      59    diethylene glycol                                                                           acetic acid   25° C.                                     dimethyl ether                                                          60    ethyl alcohol phosphoric acid                                                                             10°-25° C.                    61    ethylene glycol                                                                             phosphoric acid                                                                             -10° C.                                    monoethyl ether                                                         62    chlorobenzene aluminum chloride                                                                           reflux                                      63    toluene       zinc chloride 25° C.                               64    ethylene dichloride                                                                         stannic chloride                                                                            25° C.                               65    ethylene dichloride                                                                         thionyl chloride                                                                            25° C.                               66    chlorobenzene benzoyl peroxide                                                                            reflux                                      67    1-ethyl-2-    stannic chloride                                                                            20°-30° C.                          methylindole                                                            68    ethyl alcohol hydrobromic acid                                                                            RT                                          69    ethyl alcohol fluoroboric acid                                                                            RT                                          70    ethyl alcohol hydriodic acid                                                                              RT                                          71    ethyl alcohol nitric acid   RT                                          72    ethyl alcohol perchloric acid                                                                             RT                                          73    ethyl alcohol formic acid   RT                                          74    ethyl alcohol trifluoroacetic acid                                                                        RT                                          75    ethyl alcohol glycolic acid RT                                          76    ethyl alcohol malonic acid  RT                                          77    ethyl alcohol fumaric acid  RT                                          78    ethyl alcohol benzoic acid  RT                                          79    ethyl alcohol citric acid   RT                                          80    ethyl alcohol salicylic acid                                                                              RT                                          81    ethyl alcohol picric acid   RT                                          82    ethyl alcohol trimellitic acid                                                                            RT                                          ______________________________________                                    

Following a procedure similar to that described in Example 6 abovesubstituting for ethyl alcohol and methanesulfonic acid the appropriatereaction medium and the appropriate catalyst listed in Examples 83-109of Table B hereinbelow, 4-dimethylaminobenzaldehyde, N,N-dimethylanilineand sodium p-toluenesulfinate were interacted at the indicatedtemperature to obtain a methane of Formula XV wherein R═4--CH₃ ; R⁵ ═H,R⁶ ═N(CH₃)₂ ; Q═4--(CH₃)₂ NC₆ H₄. A toluene or acetone solution of theproduct from Examples 83-109 contacted with silica gel developed a bluecolored image.

                  TABLE B                                                         ______________________________________                                        Ex-                                Reaction                                   am-                                Temper-                                    ple  Reaction Medium  Catalyst     ature                                      ______________________________________                                        83   isopropyl alcohol                                                                              p-toluenesulfonic                                                                          80° C.                                                    acid                                                    84   acetonitrile     p-toluenesulfonic                                                                          reflux                                                           acid                                                    85   ethylene dichloride                                                                            p-toluenesulfonic                                                                          70°-75° C.                                         acid                                                    86   ethyl alcohol    sulfuric acid                                                                              reflux                                     87   water            sulfuric acid                                                                              90° C.                              88   isopropyl alcohol                                                                              sulfuric acid                                                                              reflux                                     89   water            methanesulfonic                                                                            85°-90° C.                                         acid                                                    90   ethyl alcohol    hydrochloric acid                                                                          reflux                                     91   isopropyl alcohol                                                                              hydrochloric acid                                                                          reflux                                     92   water            hydrochloric acid                                                                          reflux                                     93   ethyl alcohol    phosphoric acid                                                                            reflux                                     94   ethylene dichloride                                                                            phosphorus   25° C.                                                    trichloride                                             95   ethylene dichloride                                                                            phosphorus   25°-30° C.                                         pentachloride                                           96   N,N-dimethylformamide &                                                                        phosphorus   45°-50° C.                        isopropyl alcohol                                                                              oxychloride                                             97   acetonitrile     phosphorus   reflux                                                           oxychloride                                             98   ethylene dichloride                                                                            thionyl chloride                                                                           25° C.                              99   ethylene dichloride                                                                            boron trifluoride                                                                          reflux                                                           etherate                                                100  N,N-dimethylaniline                                                                            boron trifluoride                                                                          reflux                                                           etherate                                                101  ethylene dichloride                                                                            ferric chloride                                                                            reflux                                     102  ethylene dichloride                                                                            ferric oxide reflux                                     103  ethylene dichloride                                                                            aluminum oxide                                                                             reflux                                     104  ethylene dichloride                                                                            p-toluenesulfonic                                                                          reflux                                                           acid                                                    105  acetonitrile     benzoyl chloride                                                                           reflux                                     106  acetonitrile     phosphorus   20°-60° C.                                         pentaoxide                                              107  isopropyl crown ether                                                                          potassium    reflux                                                           fluoride                                                108  chlorobenzene    p-toluenesulfonic                                                                          80°-90° C.                                         acid                                                    109  N,N-dimethylaniline                                                                            thionyl chloride                                                                           25°-30° C.                   ______________________________________                                    

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate 2-R⁵-4-R⁶ -benzaldehyde, the appropriate 1-R¹ -2-R² -5/6-R³ -indole and theappropriate R-phenylsulfinic acid, there will be obtained the [(2-R⁵-4-R⁶ -phenyl)(1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)]methanesof Formula II, Examples 110-120, presented in Table C hereinbelow.

                                      TABLE C                                     __________________________________________________________________________    Methanes of Formula II                                                        Ex.                                                                              R      R.sup.1  R.sup.2                                                                           R.sup.3                                                                             R.sup.5                                                                           R.sup.6                                      __________________________________________________________________________    110                                                                              4-Br   2-(C.sub.2 H.sub.5)C.sub.6 H.sub.12                                                    CH.sub.3                                                                          H     CH.sub.3 O                                                                        N(CH.sub.3).sub.2                            111                                                                              2,4(CH.sub.3).sub.2                                                                  4-Cl--C.sub.6 H.sub.4 CH.sub.2                                                         CH.sub.3                                                                          5-NO.sub.2                                                                          Cl  N(CH.sub.3).sub.2                            112                                                                              2-NO.sub.2                                                                           n-C.sub.8 H.sub.17                                                                     CH.sub.3                                                                          H     CH.sub.3                                                                          N(C.sub.2 H.sub.5).sub.2                     113                                                                              3,4(Cl).sub.2                                                                        CH.sub.3 H   5-Br-6-NO.sub.2                                                                     H   i-C.sub.3 H.sub.7                            114                                                                              4-F    2-CH.sub.3 --C.sub.6 H.sub.4 CH.sub.2                                                  CH.sub.3                                                                          H     CH.sub.3 O                                                                        CH.sub.3 O                                   115                                                                              4-CH.sub.3 O                                                                         H        C.sub.2 H.sub.5                                                                   6-CH.sub.3                                                                          CH.sub.3                                                                          N(CH.sub.3) (C.sub.6 H.sub.5 CH.sub.2)       116                                                                              4-Cl,3NO.sub.2                                                                       i-C.sub.4 H.sub.9                                                                      CH.sub.3                                                                          H     Br  H                                            117                                                                              4-CH.sub.3 CONH                                                                      1-(CH.sub.3) (C.sub.6 H.sub.12)                                                        H   5-I   H   C.sub.2 H.sub.5 O                            118                                                                              3-NO.sub.2                                                                           C.sub.2 H.sub.4                                                                        CH.sub.3                                                                          H     C.sub.2 H.sub.5 O                                                                 H                                            119                                                                              2,5-(CH.sub.3).sub.2                                                                 i-C.sub. 5 H.sub.11                                                                    H   H     F   H                                            120                                                                              4-I    H        i-C.sub.3 H.sub.7                                                                 H     H   NHC.sub.6 H.sub.5 CH.sub.2                   __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate1-R^(1') -2-R^(2') -5/6-R^(3') -indole-3-carboxaldehyde, the appropriate1-R¹ -2-R² -5/6-R³ -indole and the appropriate R-phenylsulfinic acid,there will be obtained the [(1-R^(1') -2-R^(2') -5/6-R^(3')-3-indolyl)(1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)]methanes ofFormula III, Examples 121-131, presented in Table D hereinbelow.

                                      TABLE D                                     __________________________________________________________________________    Methanes of Formula III                                                       Ex.                                                                              R     R.sup.1                                                                              R.sup.2                                                                           R.sup.3                                                                             R.sup.1' R.sup.2'                                                                         R.sup.3'                                __________________________________________________________________________    121                                                                              4-Cl  C.sub.6 H.sub.5 CH.sub.2                                                             H   6-F   H        H  5-CH.sub.3 O                            122                                                                              4-NO.sub.2                                                                          H      C.sub.2 H.sub.5                                                                   5-CH.sub.3                                                                          n-C.sub.8 H.sub.17                                                                     CH.sub.3                                                                         H                                       123                                                                              2,4-(CH.sub.3).sub.2                                                                CH.sub.2 CHCH.sub.2                                                                  CH.sub.3                                                                          H     n-C.sub.4 H.sub.9                                                                      C.sub.6 H.sub.5                                                                  H                                       124                                                                              2,5-(Cl).sub.2                                                                      i-C.sub.3 H.sub.7                                                                    H   H     CH.sub.3 CH.sub.3                                                                         H                                       125                                                                              4-CH.sub.3 O                                                                        H      CH.sub.3                                                                          5,6-(CH.sub.3).sub.2                                                                H        H  H                                       126                                                                              4-I   4-BrC.sub.6 H.sub.4 CH.sub.2                                                         i-C.sub.3 H.sub.7                                                                 H     C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.5                                                                  H                                       127                                                                              2,4-(NO.sub.2).sub.2                                                                H      C.sub.6 H.sub.5                                                                   5,6(Cl).sub.2                                                                       C.sub.2 H.sub.5                                                                        CH.sub.3                                                                         H                                       128                                                                              C.sub.2 H.sub.5                                                                     n-C.sub.4 H.sub.9                                                                    H   CH.sub.3 O                                                                          C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.5                                                                  H                                       129                                                                              H     C.sub.8 H.sub.17                                                                     CH.sub.3                                                                          H     CH.sub.2 C.sub.6 H.sub.5                                                               H  5-F                                     130                                                                              CH.sub.3                                                                            C.sub. 4 H.sub.9                                                                     CH.sub.3                                                                          H     H        H  5,6-(CH.sub.3 O).sub.2                  131                                                                              4-Cl  H      C.sub.3 H.sub.7                                                                   H     1-[(CH.sub.3) (C.sub.6 H.sub.12)]                                                      H  5-I                                     __________________________________________________________________________

It is comtemplated that by following procedures similar to thosedescribed in the foregoing examples but employing an appropriate 9-R⁷-3-carbazolecarboxaldehyde or 1-R⁸ -pyrrole-2-carboxaldehyde, theappropriate R-phenylsulfinic acid and the appropriate 1-R¹ -2-R² -5/6-R³-indole, there will be obtained the [(9-R⁷ -3-carbazolyl)(1-R¹ -2-R²-5/6-R³ -3-indolyl)(R-phenylsulfonyl)]methanes of Formula IV and [(1-R⁸-2-pyrrolyl)(1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)]methanesof Formula V, Examples 132-141, presented in Table E hereinbelow.

                                      TABLE E                                     __________________________________________________________________________    Methanes of Formulas IV and V                                                 Ex.   R     R.sup.1   R.sup.2                                                                          R.sup.3                                                                            R.sup.7                                                                          R.sup.8                                      __________________________________________________________________________    132                                                                              (IV)                                                                             H     H         C.sub.2 H.sub.5                                                                  H    CH.sub.3                                                                         --                                           133                                                                              (V)                                                                              4-Cl  C.sub.4 H.sub.9                                                                         H  5-CH.sub.3 O                                                                       -- C.sub.6 H.sub.5                              134                                                                              (IV)                                                                             4-NO.sub.2                                                                          CH.sub.3  H  6-NO.sub.2                                                                         C.sub.3 H.sub.7                                                                  --                                           135                                                                              (V)                                                                              4-CH.sub.3 O                                                                        2,6-(Cl).sub.2 C.sub.6 H.sub.3 CH.sub.2                                                 CH.sub.3                                                                         H    -- C.sub.2 H.sub.5                              136                                                                              (IV)                                                                             4-Br  H         C.sub.6 H.sub.5                                                                  5,6-(Cl).sub.2                                                                     C.sub.6 H.sub.5                                                                  --                                           137                                                                              (V)                                                                              2,4(CH.sub.3).sub.2                                                                 3-(2-CH.sub.3)C.sub.3 H.sub.4                                                           CH.sub.3 O                                                                       H    -- CH.sub.3                                     138                                                                              (IV)                                                                             4-CH.sub.3 O                                                                        C.sub.6 H.sub.13                                                                        H  H    C.sub.2 H.sub.5                                                                  --                                           139                                                                              (IV)                                                                             2-NO.sub.2                                                                          H         CH.sub.3                                                                         6-Br -- C.sub.3 H.sub.7                              140                                                                              (V)                                                                              2,5(CH.sub.3).sub.2                                                                 C.sub.6 H.sub.5 CH.sub.2                                                                CH.sub.3                                                                         H    H  --                                           141                                                                              (IV)                                                                             3,4(Cl).sub.2                                                                       CH.sub.3  CH.sub.3                                                                         6-NO.sub.2                                                                         -- H                                            __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate 1-R¹-2-R² -5/6-R³ -indole, the appropriate R-phenylsulfinic acid and theappropriate aldehyde of the formula A-CHO, there will be obtained the[(A)(1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)]methanes ofFormulas VI-X, Examples 142-160, presented in Table F hereinbelow.

                                      TABLE F                                     __________________________________________________________________________    Methanes of Formulas VI-118                                                   Ex.    A         R      R.sup.1   R.sup.2                                                                           R.sup.3                                 __________________________________________________________________________    142                                                                              (VI)                                                                               ##STR35##                                                                              4-I    n-C.sub.4 H.sub.9                                                                       CH.sub.3                                                                          H                                       143                                                                              "   "         3-NO.sub.2                                                                           2,5(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2                                            CH.sub.3                                                                          H                                       144                                                                              "   "         4-CH.sub.3 O                                                                         CH.sub.3  CH.sub.3                                                                          6-NO.sub.2                              145                                                                              "   "         2,4(Cl).sub.2                                                                        i-C.sub.5 H.sub.11                                                                      H   H                                       146                                                                              "   "         2,5(CH.sub.3).sub.2                                                                  H         C.sub.6 H.sub.5                                                                   5,6(Cl).sub.2                           147                                                                              (VII)                                                                              ##STR36##                                                                              2-NO.sub.2                                                                           i-C.sub.3 H.sub.7                                                                       CH.sub.3                                                                          H                                       148                                                                              "   "         4-Br   3-ClC.sub.6 H.sub.4 CH.sub.2                                                            C.sub.2 H.sub.5                                                                   H                                       149                                                                              "   "         4-CH.sub.3 CONH                                                                      H         H   5,6-(CH.sub.3 O).sub.2                  150                                                                              "   "         2,4(CH.sub.3).sub.2                                                                  CH.sub.3  H   5-Br-6-NO.sub.2                         151                                                                              "   "         4-CH.sub.3 O                                                                         H         C.sub.2 H.sub. 5                                                                  5-CH.sub.3                              152                                                                              (VIII)                                                                             ##STR37##                                                                              3,4(Cl).sub.2                                                                        C.sub.6 H.sub.5 CH.sub.2                                                                H   5-F                                     153                                                                              "                                                                                  ##STR38##                                                                              4-F    s-C.sub.4 H.sub.9                                                                       CH.sub.3                                                                          H                                       154                                                                              "                                                                                  ##STR39##                                                                              2-NO.sub.2                                                                           C.sub.2 H.sub.4                                                                         CH.sub.3                                                                          H                                       155                                                                              "   "         2,5(CH.sub.3).sub.2                                                                  CH.sub.3  CH.sub.3                                                                          6-NO.sub.2                              156                                                                              "                                                                                  ##STR40##                                                                              4-CH.sub.3 O                                                                         C.sub.8 H.sub.17                                                                        CH.sub.3                                                                          H                                       157                                                                              (IX)                                                                               ##STR41##                                                                              4-Cl-3-NO.sub.2                                                                      H         C.sub.2 H.sub.5                                                                   6-CH.sub.3                              158                                                                              "   "         4-Br   C.sub.6 H.sub.13                                                                        CH.sub.3                                                                          H                                       159                                                                              "   "         3-NO.sub.2                                                                           4-BrC.sub.6 H.sub.4 CH.sub.2                                                            i-C.sub.3 H.sub.7                                                                 H                                       160                                                                              "   "         4-CH.sub.3 O                                                                         CH.sub.3  H   6-NO.sub.2                              __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate R⁴(CH₂)_(n) CHO, the appropriate 1-R¹ -2-R² -5/6-R³ -indole and theappropriate R-phenylsulfinic acid, there will be obtained the {[R⁴(CH₂)_(n) ](1-R¹ -2-R² -5/6-R³ -3-indolyl)(R-phenylsulfonyl)} methanesof Formula X, Examples 161-170, presented in Table G hereinbelow.

                  TABLE G                                                         ______________________________________                                        Methanes of Formula X                                                         Ex.  R          R.sup.1  R.sup.2                                                                            R.sup.3 R.sup.4                                                                             n                                 ______________________________________                                        161  4-CH.sub.3 n-C.sub.4 H.sub.9                                                                      CH.sub.3                                                                           H       CH.sub.3                                                                            0                                 162  4-Br       H        C.sub.6 H.sub.5                                                                    H       CH.sub.3                                                                            2                                 163  2,4-(CH.sub.3).sub.2                                                                     C.sub.6 H.sub.5 CH.sub.2                                                               H    5-F     CH.sub.3                                                                            8                                 164  2-NO.sub.2 CH.sub.3 H    6-NO.sub.2                                                                            CH.sub.3                                                                            4                                 165  4-CH.sub.3 CONH                                                                          C.sub.8 H.sub.17                                                                       CH.sub.3                                                                           H       CH.sub.3                                                                            5                                 166  4-Cl       CH.sub.3 C.sub.2 H.sub.5                                                                    H       CH.sub.3                                                                            6                                 167  4-CH.sub.3 O                                                                             CH.sub.3 H    5-Br-6-NO.sub.2                                                                       CH.sub.3                                                                            1                                 168  H          C.sub.2 H.sub.4                                                                        CH.sub.3                                                                           H       CH.sub.3                                                                            3                                 169  2,5(Cl).sub.2                                                                            H        H    5,6(CH.sub.3 O).sub.2                                                                 CH.sub.3                                                                            7                                 170  3-NO.sub.2 i-C.sub.5 H.sub.11                                                                     CH.sub.3                                                                           H       CH.sub.3                                                                            2                                 ______________________________________                                    

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate(CH₂)m(CHO)₂ or 2,5-dimethoxytetrahydrofuran for those products in whichm=2, the appropriate 1-R¹ -2-R² -5/6-R³ -indole and the appropriateR-phenylsulfinic acid, there will be obtained the [α,ω-bis(1-R¹ -2-R²-5/6-R³ -3-indolyl)-α,ω-bis(R-phenylsulfonyl)]alkanes of Formula XI,Examples 171-180, presented in Table H hereinbelow.

                                      TABLE H                                     __________________________________________________________________________    Alkanes of Formula XI                                                         Ex. R      R.sup.1   R.sup.2                                                                            R.sup.3                                                                              m                                            __________________________________________________________________________    171 4-CH.sub.3                                                                           H         H    H      2                                            172 4-CH.sub.3 O                                                                         C.sub.8 H.sub.17                                                                        CH.sub.3                                                                           H      2                                            173 2-NO.sub.2                                                                           H         i-C.sub.3 H.sub.7                                                                  H      3                                            174 3,4-(Cl).sub.2                                                                       2,5-(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2                                           CH.sub.3                                                                           H      2                                            175 4-I    H         C.sub.2 H.sub.5                                                                    6-CH.sub.3                                                                           3                                            176 H      1-CH.sub.3 C.sub.6 H.sub.12                                                             H    5-I    3                                            177 4-CH.sub.3 CONH                                                                      H         C.sub.6 H.sub.5                                                                    6-Cl   2                                            178 2,5-(CH.sub.3).sub.2                                                                 CH.sub.3  H    5-Br-6-NO.sub.2                                                                      3                                            179 4-Br   n-C.sub.4 H.sub.9                                                                       CH.sub.3                                                                           H      3                                            180 3-NO.sub.2                                                                           C.sub.2 H.sub.4                                                                         CH.sub.3                                                                           H      2                                            __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate 2-R⁵-4-R⁶ -benzaldehyde, the appropriate compound of the formula Q-H and theappropriate R-phenylsulfinic acid, there will be obtained the [(Q)(2-R⁵-4-R⁶ -phenyl)(R-phenylsulfonyl]methanes of Formula XV, Examples181-198, presented in Table I hereinbelow.

                                      TABLE I                                     __________________________________________________________________________    Methanes of Formula XV                                                        Ex.                                                                              Q              R     R.sup.5                                                                           R.sup.6                                           __________________________________________________________________________    181                                                                              2,4-bis[(CH.sub.3).sub.2 N]C.sub.6 H.sub.3                                                   4-CH.sub.3                                                                          Cl  H                                                 182                                                                              4-(C.sub.3 H.sub.7).sub.2 NC.sub.6 H.sub.4                                                   4-Cl  H   CH.sub.3 O                                        183                                                                              3-CH.sub.3 --4(CR.sub.3).sub.2 NC.sub.6 H.sub.3                                              2-NO.sub.2                                                                          C.sub.2 H.sub.5 O                                                                 H                                                 184                                                                              3-CH.sub.3 O-4(C.sub.2 H.sub.5).sub.2 NC.sub.6 H.sub.3                                       H     CH.sub.3 O                                                                        CH.sub.3 O                                        185                                                                              9-julolidinyl  2,5-(CH.sub.3).sub.2                                                                Cl  N(CH.sub.3).sub.2                                 186                                                                              2-C.sub.2 H.sub.5 O--4-(C.sub.2 H.sub.5).sub.2 NC.sub.6 H.sub.3                              4-CH.sub.3                                                                          H   i-C.sub.3 H.sub.7                                 187                                                                              2,4-bis[(C.sub.2 H.sub.5).sub.2 N]C.sub.6 H.sub.3                                            3,4-(Cl).sub.2                                                                      CH.sub.3 O                                                                        N(C.sub.2 H.sub.5).sub.2                          188                                                                              2-Cl--4-(i-C.sub.3 H.sub.7).sub.2 NC.sub.6 H.sub.3                                           4-I   H   N(CH.sub.3)(C.sub.6 H.sub.5 CH.sub.2)             189                                                                              2-I-4(C.sub.4 H.sub.9) (C.sub.6 H.sub.5 CH.sub.2)NC.sub.6 H.sub.3                            4-CH.sub.3 O                                                                        Br  H                                                 190                                                                              2-CH.sub.3 --4-(C.sub.2 H.sub.5).sub. 2 NC.sub.6 H.sub.3                                     3-NO.sub.2                                                                          H   N(H) (C.sub.6 H.sub.5 CH.sub.2)                   191                                                                              4-(C.sub.2 H.sub.5) (C.sub.6 H.sub.5 CH.sub.2) NC.sub.6 H.sub.3                              H     CH.sub.3                                                                          N(C.sub.2 H.sub.5).sub.2                          192                                                                              2-C.sub.3 H.sub.7 O-4-(C.sub.2 H.sub.5).sub.2 NC.sub.6 H.sub.3                               4-Br  F   H                                                 193                                                                              4-(CH.sub.3) (C.sub.3 H.sub.7)NC.sub.6 H.sub.4                                               4-C1-3-NO.sub.2                                                                     CH.sub.3 O                                                                        H                                                 194                                                                              2,4-bis[(C.sub.4 H.sub.9).sub.2 N]C.sub.6 H.sub.3                                            4-CH.sub.3                                                                          H   C.sub.2 H.sub.5 O                                 195                                                                              2-(i-C.sub.3 H.sub.7)--4-(C.sub.2 H.sub.5).sub.2 NC.sub.6 H.sub.3                            H     CH.sub.3 O                                                                        N(CH.sub.3).sub.2                                 196                                                                              4-(CH.sub.3).sub.2 NC.sub.6 H.sub.4                                                          4-F   H   N(C.sub.2 H.sub.5).sub.2                          197                                                                              2,4-bis[(CH.sub.3).sub.2 N]C.sub.6 H.sub.3                                                   4-CH.sub.3                                                                          H   CH.sub.3                                          198                                                                              9-julolidinyl  H     H   Cl                                                __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriatealdehyde of the formula Z-CHO, the appropriate 1-R⁸ -pyrrole and theappropriate R-phenylsulfinic acid, there will be obtained the [(Z)(1-R⁸-2-pyrrolyl)(R-phenylsulfonyl)]methanes of Formulas XVII--XX, Examples199-228, presented in Table J hereinbelow.

                  TABLE J                                                         ______________________________________                                        Methanes of Formulas XVII-XX                                                  Ex.   Z                 R           R.sup.8                                   ______________________________________                                        199   2-ClC.sub.6 H.sub.4                                                                             4-CH.sub.3  C.sub.6 H.sub.4                           200   4-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                              4-H         C.sub.3 H.sub.7                           201   2,4-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3                                                          4-Cl        C.sub.2 H.sub.5                           202   4-i-C.sub.3 H.sub.7 C.sub.6 H.sub.4                                                             4-Cl-3-NO.sub.2                                                                           i-C.sub.3 H.sub.7                         203   4-(CH.sub.3).sub.2 NC.sub.6 H.sub.4                                                             4-Br        CH.sub.3                                  204   2-CH.sub.3 O-4-(C.sub.2 H.sub.5).sub.2 NC.sub.6 H.sub.3                                         4-CH.sub.3 O                                                                              H                                         205   4-(CH.sub.3) (C.sub.6 H.sub.5 CH.sub.2)NC.sub.6 H.sub.4                                         4-I         C.sub.3 H.sub.7                           206   2-Cl-4(CH.sub.3).sub.2 NC.sub.6 H.sub.3                                                         4-CH.sub.3 CONH                                                                           C.sub.6 H.sub.5                           207   1-CH.sub.3 -2-pyrrolyl                                                                          4-CH.sub.3  CH.sub.3                                  208   2-pyrrolyl        4-CH.sub.3 O                                                                              C.sub.2 H.sub.5                           209   1-ethyl-2-pyrrolyl                                                                              4-C.sub.12 H.sub.25                                                                       i-C.sub.3 H.sub.7                         210   1-i-propyl-2-pyrrolyl                                                                           4-Cl        C.sub.3 H.sub.7                           211   2-thienyl         2,4-(CH.sub.3).sub.2                                                                      C.sub.6 H.sub.5                           212   2-thienyl         3-NO.sub.2  H                                         213   2-thienyl         2,5-(Cl).sub.2                                                                            C.sub.2 H.sub.5                           214   2-thienyl         H           C.sub.6 H.sub.4                           215   2-furanyl         4-CH.sub.3 CONH                                                                           CH.sub.3                                  216   2-furanyl         4-F         C.sub.2 H.sub.5                           217   2-furanyl         2,5-(CH.sub.3).sub.2                                                                      C.sub.6 H.sub.5                           218   2-furanyl         4-I         i-C.sub.3 H.sub.7                         219   3-carbazolyl      4-C.sub.12 H.sub.25                                                                       CH.sub.3                                  220   9-phenyl-3-carbazolyl                                                                           4-Br        C.sub.2 H.sub.5                           221   9-ethyl-3-carbazolyl                                                                            2-NO.sub.2  C.sub.6 H.sub.5                           222   9-propyl-3-carbazolyl                                                                           3,4-(Cl).sub.2                                                                            C.sub.3 H.sub.7                           223   2-pyridinyl       4-CH.sub.3  H                                         224   3-pyridinyl       3-NO.sub.2  CH.sub.3                                  225   4-pyridinyl       4-Cl        C.sub.2 H.sub.5                           226   2-pyridinyl       4-Cl-3-NO.sub.2                                                                           i-C.sub.3 H.sub.7                         227   3-pyridinyl       4-C.sub.12 H.sub.25                                                                       C.sub.6 H.sub.5                           228   4-pyridinyl       H           C.sub.3 H.sub.7                           ______________________________________                                    

EXAMPLE 229

The use of the compounds of Formulas I, XI, XV and XVI described inExamples 1 through 228 as color forming components in pressure sensitivemicroencapsulated copying systems is illustrated with reference to theproduct of Example 1.

A. A mixture of 40 g of i-propylbiphenyl and 0.98 g of[(1-ethyl-2-methyl-3-indolyl)-(4-dimethylaminophenyl)-(4-methylphenylsulfonyl)]methane,prepared as described above in Example 1 was heated to 100° C. until aclear solution was formed and then cooled to approximately 50° C. Asecond solution of 3.35 g of carboxymethylcellulose dissolved in 134 mlof distilled water was prepared. A third solution containing 10 g ofpigskin gelatin dissolved in 80 ml of distilled water was heated atapproximately 50° C. for about one hour.

B. Two solutions, the first containing the product and thei-propylbiphenyl, and the second containing the carboxymethylcelluloseand the water were mixed and emulsified using a variable speed one-halfhorsepower Eppenbach Homo-Mixer (Gifford-Wood Co., Hudson, N.Y.) forapproximately five minutes until the particle size of the suspendedemulsion was approximately 5 microns at approximately 50° C. Whilemaintaining the rapid agitation, the third solution containing thegelatin and water was added and the pH adjusted to 6.5 with the additionof 10 percent aqueous sodium hydroxide. Slowly 447 ml of water atapproximately 50° C. was added and the pH was adjusted to 4.5 by theaddition of 10 percent aqueous acetic acid. After five minutes of rapidagitation the mixture was cooled to approximately 15° C. by means of anexternal ice/water bath and 6.6 ml of glutaraldehyde was added dropwiseand agitation continued for 15 minutes. At this time, the EppenbachHomo-Mixer was replaced with a conventional blade type laboratoryagitator and the suspension was stirred overnight. The suspension wasadjusted to 747 g with the addition of distilled water.

C. The stock microcapsule suspension prepared in part B above was coatedon paper sheets to a thickness of approximately 0.0015 inch and thecoated paper air dried. The paper thus coated with the microencapsulatedcolorless precursor was assembled as the top sheet in a manifold systemby positioning the coated side in contact with the coated side of acommercially available receiving sheet coated with a color developer ofthe electron accepting type. More specifically, papers coated with aphenolic resin and with an acidic clay were employed in this test. Animage was then drawn with a stylus on the top sheet bearing themicroencapsulated colorless precursor on its reverse side causing theaffected microcapsules to rupture thus allowing the solution of thecolorless precursor held by said microcapsules to flow into contact withthe color developing substance on the receiving sheet whereupon abluish-red-colored image promptly formed. The developed image exhibitedgood tinctorial strength and excellent xerographic copiabilitycharacteristics.

When evaluated in a duplicating system prepared and tested as describedabove, the product of Example 18,[(2-furanyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane,produced a yellow-colored image; the product of Example 19,[(2-thienyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane,produced a yellow-colored image; the product of Example 8,[(1-methyl-2-pyrrolyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane,produced a yellow-colored image; the product of Example 21,[bis(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane,produced an orange-colored image; and the product of Example 22,[(3-indolyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane,produced an orange-colored image.

EXAMPLE 230

The utility of the compounds of Formulas I, XV and XVI whosepreparations are described in the foregoing examples as color formingcomponents in pressure-sensitive microencapsulated copying systems, isillustrated by the incorporation and testing of the compound of Example1,[(1-ethyl-2-methyl-3-indolyl)(4-dimethylaminophenyl)(4-methylphenylsulfonyl)]methanein a pressure-sensitive marking paper. The test paper was prepared by aprocedure described in U.S. Pat. 4,000,087.

A. A mixture of 5.9 g of a commercially-supplied polyvinyl alcoholhaving a hydrolysis of 87 to 89 percent and 250.0 ml of water werewarmed until a clear solution was obtained. After cooling to roomtemperature, 40.0 ml of water was added.

B. A second solution was prepared by warming 5.9 g of acommercially-supplied epichlorohydrin/bisphenol A type solid epoxy resinin 41.8 g of dibutylphthalate until a clear solution resulted. Aftercooling slightly 3.0 g of[(1-ethyl-2-methyl-3-indolyl)(4-dimethylaminophenyl)(4-methylphenylsulfonyl)]methane,prepared as described in Example 1 above, was added and stirred untildissolved.

C. A mixture of 9.7 g of terephthaloyl chloride and 47.3 g ofdibutylphthalate was heated until a clear solution resulted and thencooled to room temperature.

D. The dye-resin solution from part B above and the terephthaloylchloride solution from part C above were mixed together and slowly addedto the polyvinyl alcohol from part A above and emulsified with avariable speed one-half horsepower Eppenbach Homo-Mixer (Gifford-WoodCo., Hudson, N.Y.) for approximately one minute at an applied voltage of30-40 until the particle size of the suspended emulsion wasapproximately 5 microns. The resulting emulsion was transferred to asuitable container with a variable speed conventional mechanical stirrerwith a 50.0 ml of water wash. With stirring there was slowly added tothe emulsion a solution consisting of 2.9 g of sodium carbonate and 5.5g of diethylene triamine dissolved in 33.0 ml of water. The resultingsuspension was stirred at room temperature for approximately eighteenhours. The pH was adjusted to 7-7.5 by the addition of 15 percentaqueous sodium carbonate and the stirring continued for approximatelysix hours. The total weight of the suspension was adjusted to 474 g withthe addition of water if needed.

E. The stock microcapsule suspension prepared in part D above was coatedon paper sheets using a #6 wire wound rod and the coated paper airdried. The paper thus coated with the microencapsulated colorlessprecursortwas assembled as the top sheet in a manifold system bypositioning the coated side in contact with the coated side of acommercially available receiving sheet coated with a color developer ofthe electron accepting type. More specifically, papers coated with aphenolic resin and with an acidic clay were employed in this test. Animage was then drawn with a stylus on the top sheet bearing themicroencapsulated colorless precursor on its reverse side causing theaffected microcapsules to rupture thus allowing the solution of thecolorless precursor held by said microcapsules to flow into contact withthe color developing substance on the receiving sheet whereupon abluish-red-colored image promptly formed. The developed image exhibitedgood tinctorial strength and excellent xerographic copiabilitycharacteristics.

When evaluated in a duplicating system prepared and tested as describedabove, the product of Example 18,[(2-furanyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane,produced a yellow-colored image; the product of Example 19,[(2-thienyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane,produced a yellow-colored image; the product of Example 8,[(1-methyl-2-pyrrolyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane,produced a yellow-colored image; the product of Example 21,[bis(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane,produced an orange-colored image; the product of Example 22,[(3-indolyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methane,produced an orange-colored image; the product of Example 6,[bis(4-dimethylaminophenyl)(4-methylphenylsulfonyl)]methane, produced ablue-colored image; and the product of Example 39,[(4-dimethylaminophenyl)(2-ethoxy-4-diethylaminophenyl)(4methylphenylsulfonyl)]methane,produced a blue-colored image.

EXAMPLE 231

The utility of the compounds of Formulas I, XI, XV, and XVI whosepreparations are described in the foregoing examples as color formingcomponents in thermal marking systems is illustrated by theincorporation and testing of the compound of Example 1,[(1-ethyl-2-methyl-3-indolyl)-(4-dimethylaminophenyl)-(4-methylphenylsulfonyl)]methanein a thermal sensitive marking paper. The test paper was prepared by aprocedure similar to that described in U.S. Pat. No. 3,539,375.

A. A mixture of 2.0 g of[(1-ethyl-2-methyl-3-indolyl)(4-dimethylaminophenyl)-(4-methylphenylsulfonyl)]methane,8.6 g of a ten percent aqueous solution of polyvinyl alcohol(approximately 99 percent hydrolyzed), 3.7 g of water and 31.6 g of 1/16inch diameter zirconium grinding beads was charged into a containerwhich was placed in a mechanical shaker. Shaking was effected for onehour. The zirconium beads were then removed by straining the mixturethrough a No. 40 sieve.

B. Similarly, a mixture of 9.8 g of 4,4'-isopropylidine diphenol(Bisphenol A), 42.0 g of a ten percent aqueous polyvinyl alcoholsolution (approximately 99 percent hydrolyzed), 18.2 g of water and221.2 g of 1/16 inch diameter zirconium grinding beads was charged intoa container which was placed in a mechanical shaker. After shaking waseffected for one hour, the zirconium beads were removed by strainingthrough a No. 40 sieve.

C. A coating composition was prepared by mixing 2.1 g of the slurry fromA and 47.9 g of the slurry from B. The mixture was then uniformly coatedon sheets of paper at a thickness of approximately 0.0015 inch and thecoated sheets air-dried. The coated paper was tested by tracing a designon the coated side of the paper placed on a smooth flat surface with astylus heated to approximately 120° C. A violet-colored imagecorresponding to the traced design promptly developed.

When evaluated in thermal marking paper prepared and tested as describedabove, the product of Example 19,[(2-thienyl)-(1-ethyl-2-methyl-3-indolyl)-(4-methylphenylsulfonyl)]methane,produced a light yellow-colored image at approximately 180° C.; theproduct of Example 2,[(1,2-dimethyl-3-indolyl)-(4-dimethylaminophenyl)-(4-methylphenylsulfonyl)]methane,produced a reddish-purple-colored image at approximately 105° C.; theproduct of Example 21,[bis(1-ethyl-2-methyl-3-indolyl)-(4-methylphenylsulfonyl)]methane,produced an orange-colored image at approximately 105° C. and aviolet-red-colored image at 150° C.; the product of Example 8,[(1-methyl-2-pyrrolyl)-(4-dimethylaminophenyl)-(4-methylphenylsulfonyl)]methane,produced a reddish-orange-colored image at approximately 100° C.; theproduct of Example 10,[(2-phenyl-3-indolyl)-(4-dimethylaminophenyl)-(4-methylphenylsulfonyl)]methane,produced a blue-colored image at approximately 100° C.; the product ofExample 38,[(4-dimethylaminophenyl)(4-N-ethyl-N-benzylaminophenyl)(4-methyphenylsulfonyl)]methane,produced a turquoise-colored image at approximately 160° C.; the productof Example 49,[(4-chlorophenyl)(1-methyl-2-pyrrole)(4-methylphenylsulfonyl)]methane,produced a rust-colored image; the product of Example 51,[(4-methoxyphenyl)(1-methyl-2-pyrrolyl))(benzenesulfonyl)]methane,produced an orange-colored image at 150° C.; the product of Example 55,[(2-thienyl)(1-methyl-2-pyrrolyl)(4-methylphenylsulfonyl)]methane,produced a pinkish-brown colored image at 150° C.; and the product ofExample 57,[(9-ethyl-3-carbazolyl)(1-methyl-2-pyrrolyl)(4-methylphenylsulfonyl)]methane,produced a purple-red-colored image.

EXAMPLE 232

A. Proceeding in a manner similar to that described in Example 231above, 2.0 g of the compound of Example 4,[(3-indolyl)(4-methylphenylsulfonyl)]methane was ground in a mixture of8.6 of a ten percent aqueous solution of polyvinyl alcohol and 3.7 g ofwater.

B. A mixture of 9.8 g of 4,4'-isopropylidine diphenol (bisphenol A),42.0 g of ten percent aqueous polyvinyl alcohol, 22.1 g of water and221.6 g of 1/16 inch diameter zirconium grinding beads was ground forapproximately one hour.

C. A coating composition was prepared by mixing 2.1 g of the slurry fromA and 47.9 g of the slurry from B. The mixture was then uniformly coatedon sheets of paper at a thickness of approximately 0.0015 inch and thecoated sheets air-dried. The coated paper was tested by tracing a designon the coated side of the paper placed on a smooth flat surface with astylus heated to approximately 130° C. A light blue-colored imagecorresponding to the traced design promptly developed.

When evaluated in thermal marking paper prepared and tested as describedabove, the product of Example 3,[(1-ethyl-2-methyl-3-indolyl)-(methyl)-(4-methylphenylsulfonyl)]methane,produced a light grape-colored image at approximately 130° C.

We claim:
 1. A [(2-R⁵ -4-R⁶ -phenyl)(1-R¹ -2-R² -5/6-R³-3-indolyl)(R-phenylsulfonyl)]methane of the formula ##STR42## wherein:R represents one or two of hydrogen, C₁ to C₁₂ alkyl, C₁ to C₃ alkoxy,halo, nitro or acetamido;R¹ represents hydrogen, C₁ to C₁₈ alkyl, C₂ toC₄ alkenyl, benzyl or benzyl substituted in the benzene ring by one ortwo of halo or C₁ to C₃ alkyl; R² represents hydrogen, C₁ to C₃ alkyl orphenyl; R³ represents one or two of hydrogen, C₁ to C₃ alkyl, C₁ to C₃alkoxy, halo or nitro; R⁵ represents hydrogen, dialkylamino in whichalkyl is non-tertiary C₁ to C₄ alkyl, C₁ to C₃ alkyl, C₁ to C₄ alkoxy orhalo; and R⁶ represents hydrogen, C₁ to C₃ alkyl, C₁ to C₃ alkoxy, halo,dialkylamino in which alkyl is non-tertiary C₁ to C₄ orN-alkylbenzylamino in which alkyl is non-tertiary C₁ to C₄ and benzylmay be substituted in the benzene ring by one or two of halo or C₁ to C₃alkyl. 2.[(4-Dimethylaminophenyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methaneaccording to claim
 1. 3.[(4-Dimethylaminophenyl)(1,2-dimethyl-3-indolyl)(4-methylphenylsulfonyl)]methaneaccording to claim
 1. 4.[(4-Dimethylaminophenyl)(1-ethyl-2-methyl-3-indolyl)(phenylsulfonyl)]methaneaccording to claim
 1. 5.[(4-Methoxyphenyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methaneaccording to claim
 1. 6.[(4-Dimethylaminophenyl)(2-phenyl-3-indolyl)(4-methylphenylsulfonyl)]methaneaccording to claim
 1. 7.[(4-Dimethylaminophenyl)(3-indolyl)(4-methylphenylsulfonyl)]methaneaccording to claim
 1. 8.[(4-Dimethylaminophenyl)(2,5-dimethyl-3-indolyl)(4-methylphenylsulfonyl)]methaneaccording to claim
 1. 9.[(4-Chlorophenyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methaneaccording to claim
 1. 10.[(4-Methylphenyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methaneaccording to claim
 1. 11.[(4-N-Ethyl-N-benzylaminophenyl)(1-ethyl-2-methyl-3-indolyl)(4-methylphenylsulfonyl)]methaneaccording to claim
 1. 12.[(4-Dimethylaminophenyl)(1,2-dimethyl-3-indolyl)(4-methoxyphenylsulfonyl)]methaneaccording to claim
 1. 13.[(4-Dimethylaminophenyl)(1-ethyl-2-methyl-3-indolyl)(4-chlorophenylsulfonyl)]methaneaccording to claim
 1. 14.[(4-Dimethylaminophenyl)(1-ethyl-2-methyl-3-indolyl)(4-dodecylphenylsulfonyl)]methaneaccording to claim
 1. 15.[(4-Dimethylaminophenyl)(1-ethyl-2-methyl-3-indolyl)(4-acetamidophenylsulfonyl)]methaneaccording to claim 1.